Polymeric compositions and processes for molding articles

ABSTRACT

The present invention is directed to a polymeric article comprising a blend of (a) a first polymeric component; (b) a second polymeric component the second polymeric component including an α-olefin multilock interpolymer present in the amount of about 20 percent or less by weight of the second polymeric component; and (c) at least one reinforcement material; wherein the concentration of the second polymeric component is greater than about 20 wt. % based on the total concentration of the first polymeric component and the second polymeric component. The polymeric articles desirably have one or more of the following characteristics: a soft touch feel, a low gloss appearance, or a high surface durability.

CLAIM OF PRIORITY

The present application claims the benefit of U.S. Provisional PatentApplication No. 60/981,658 (filed on Oct. 22, 2007) which is herebyincorporated by reference in its entirety for all purposes.

FIELD OF THE INVENTION

The present invention relates to an improved polyolefin composition andprocesses regarding the same. More particularly, the present inventionrelates to blended polyolefinic materials which after molding provide ahigh quality surface appearance and/or improved durability.Specifically, the present invention relates to polymeric compositionssuitable for molding articles in color having with one, two, three, oreven all of the following characteristics: low gloss, good glossuniformly, highly durable surface quality and a soft-touch tactile feel.

BACKGROUND OF THE INVENTION

Much effort has been put into developing polymeric compositions thatexhibit desirable properties, lower costs, or both. For someapplications, it is desirable to improve one or more of the following:the tactile characteristics of the polymeric articles the low glosssurface appearance, or the durability characteristics. For instance,vehicle passengers contact various automotive interior articles and itis desirable to employ a material for these articles that has a softtouch tactile sensation and is durable and withstanding frequenttouching and scratching. Among the ways to impart a soft touch feel, lowgloss appearance and high surface durability is to use a multi stepprocess applying a secondary layer of functional material on top of amolded article through overmoulding, painting or other technique. Otherways to impart a soft touch feel, low gloss appearance and high surfacedurability is a modification of a thermoplastic material to suit thedesired properties.

Examples of prior polymeric compositions and processes of forming thosecompositions are discussed in: U.S. Pat. Nos. 6,300,419; 6,949,605;6,498,214, U.S. Patent Publication 2005/0288393, and WIPO Publication2007/025663A1 all of which are hereby expressly incorporated byreference for all purposes.

U.S. Patent Application Publication No. 2007/0010616, PCT ApplicationNos. PCT/US2005/008917 (filed on Mar. 17, 2005), and PCT InternationalPatent Application Publication Nos. WO2006/102165A2 (filed Mar. 15,2000), WO2006/101966A1 (filed Mar. 15, 2006), WO2006101932A2 (filed Mar.15, 2006), and WO2006102155A2 (filed Mar. 15, 2006), all of which areexpressly incorporated herein by reference in there entirety, describeblock (i.e., blocky) copolymers of a lower α-olefin (LOA) and a secondα-olefin (i.e., LOA/α-olefin interpolymers such as ethylene/α-olefininterpolymers) which may be soft thermoplastics and blends withpolypropylene having improved mechanical properties.

PCT International Patent Application Publication No. WO2003/040201 A1(filed on May 6, 2002), published US Patent Application No. 2003/0204017(filed on May 5, 2002), European Patent No. 0495009 (filed on Dec. 12,1989), European Patent Application No. 129368 (filed on Jun. 5, 1984)and U.S. Pat. No. 6,525,157 (issued on Feb. 25, 2003), U.S. Pat. No.6,403,692 (issued Jun. 11, 2002), and U.S. Pat. No. 5,272,236 (issuedDec. 21, 1983) all of which are expressly incorporated herein byreference in there entirety, describe linear or substantially linearethylene polymers (S/LEP) which may be soft thermoplastics and polymericblends including a S/LEP.

International Patent Application Publication WO 03/040201 A1 filed onMay 6, 2002, published US Application No. 2003/020407 filed on May 5,2002, and U.S. Pat. No. 6,525,157 issued on Feb. 25, 2003, all of whichare incorporated by reference, describe polypropylene elastomers whichmay be soft thermoplastics, and polymeric blends using a propyleneelastomer.

Still, it remains desirable to provide a polymeric composition,particularly, a shaped thermoplastic polyolefin composition that canexhibit a relatively soft-touch feel and withstand the conditionsencountered in vehicle interior applications, such as substantially lowgloss, mar resistance, scratch resistance, low temperature ductility,dimensional stability, or any combination thereof. It would beparticularly attractive to accomplish this without the need to userelatively high cost or highly processed (e.g. grafted) polymers,specialty fillers or agents, or other additional or alternativerelatively costly ingredients, processes, multi-layered structures (suchas coatings) or the like while still maintaining desirablecharacteristics.

SUMMARY OF THE INVENTION

In one aspect, the invention is directed at a soft-touch feel polymericcomposition comprising a blend of: a first polymeric component includinga relatively hard thermoplastic; a second polymeric component includinga relatively soft thermoplastic, wherein the relatively softthermoplastic is a lower-α-olefin/α-olefin interpolymer (LOA/α-olefininterpolymer) which is a multiblock copolymer having one or more hardblocks and one or more soft blocks; and at least one reinforcementmaterial, wherein the concentration of the second polymeric component isgreater than about 10 wt. % (e.g., greater than about 20 wt. %) based onthe total concentration of the first polymeric component and the secondpolymeric component.

This aspect of the invention may be further characterized by one or anycombination of the following features: the LAO/α-olefin interpolymer hasat least two hard blocks and at least two soft blocks; the LAO/α-olefininterpolymer is a LAO/α-olefin interpolymer containing a lower-α-olefin(LOA) which is ethylene or propylene and at least one second differentα-olefin having 3 to 12 carbon atoms, and the LAO/α-olefin interpolymeris characterized by one or any combination of the following: theLAO/α-olefin interpolymer has a Mw/Mn from about 1.7 to about 3.5, atleast one melting point, Tm, in degrees Celsius, and a density, d, ingrams/cm³, wherein d≦0.900, and the numerical values of Tm and dcorrespond to the relationship: Tm≧1000(d)−790 (e.g.,Tm>−2002.9+4538.5(d)−2422.2(d)²), the LAO/α-olefin interpolymer has aMw/Mn from about 1.7 to about 3.5, and is characterized by a heat offusion, ΔH in J/g, and a delta quantity, ΔT, in degrees Celsius definedas the temperature difference between the tallest DSC peak and thetallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH have thefollowing relationships: ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zeroand up to 130 J/g, ΔT≧48° C. for ΔH greater than 130 J/g, wherein theCRYSTAF peak is determined using at least 5 percent of the cumulativepolymer, and if less than 5 percent of the polymer has an identifiableCRYSTAF peak, then the CRYSTAF temperature is 30° C., the LAO/α-olefininterpolymer is characterized by an elastic recovery, Re, in percent at300 percent strain and 1 cycle measured with a compression-molded filmof the LAO/α-olefin interpolymer, and has a density, d, in grams/cm³,wherein the numerical values of Re and d satisfy the followingrelationship when ethylene/α-olefin interpolymer is substantially freeof a cross-linked phase: Re>1481-1629(d), the LAO/α-olefin interpolymerhas a molecular faction which elutes between 40° C. and 130° C. whenfractionated using TREF, characterized in that the fraction has a molarcomonomer content of at least 5 percent higher than that of a comparablerandom copolymer fraction eluting between the same temperatures, whereinsaid comparable random copolymer has the same comonomer(s) and has amelt index, density, and molar comonomer content (based on the wholepolymer) within 10 percent of that of the LAO/α-olefin interpolymer, theLAO/α-olefin interpolymer has a weighted average blocking index, ABI,from about 0.15 to about 0.80, or the LAO/α-olefin interpolymer has amelt index ratio, I₁₀/I₂, from about 5 to about 35, wherein I₂ is themelt index measured according to ASTM D1238 Condition 190° C./2.16 kgwhen the LAO is ethylene and ASTM D1238 Condition 230° C./2.16 kg whenthe LAO is propylene, and I₁₀ is the melt index measured according toASTM D1238 Condition 190° C./10 kg when the LAO is ethylene and ASTMD1238 Condition 230° C./10 kg than the LAO is propylene; theLAO/α-olefin interpolymer is an ethylene/α-olefin interpolymer (e.g., anethylene/octene interpolymer); the LAO/α-olefin interpolymer is apropylene/α-olefin interpolymer (e.g., a propylene/butene interpolymer);the LAO/α-olefin interpolymer is a copolymer of ethylene and 1-octane,wherein the sum of the concentrations of the ethylene and 1-octanemonomers is greater than 95 wt. % based on the total weight of theLAO/α-olefin interpolymer; the LAO/α-olefin interpolymer ischaracterized by a density from about 0.850 to about 0.895 g/cm³(preferably from about 0.86 to about 0.89 g/cm³, more preferably from0.865 to 0.888 g/cm³); the LAO/α-olefin interpolymer is characterized bya Shore A hardness from about 15 to about 95 (preferably from about 40to about 90, more preferably from about 55 to about 90, and mostpreferably from about 70 to about 90); the LAO/α-olefin interpolymer ischaracterized by a melt index ratio, I₁₀/I₂, from about 5 to about 35(preferably from about 5.5 to about 25, more preferably from about 6 toabout 10); the LAO/α-olefin interpolymer is characterized by a meltindex ratio, I₁₀/I₂, from about 5 to about 35 (preferably from about 5.5to about 25, more preferably from about 6 to about 10) and/or a meltindex, I₂, from about 0.2 to about 100 g/10 min (preferably from about0.2 to about 40, more preferably from about 0.5 to about 10; theLAO/α-olefin interpolymer is characterized by a polydispersity index,Mw/Mn, defined by the ratio of the weight average molecular weight, Mw,and the number average molecular weight, Mn, from about 1.9 to about 7(preferably from about 2 to about 5, and more preferably from about 2 toabout 3); LAO/α-olefin interpolymer is characterized by a concentrationof soft blcok(s) from about 40 to about 95 wt. % (preferably from about50 to about 95 wt. %, and more preferably from about 60 to about 90 wt.%) based on the total weight of the LAO/α-olefin interpolymer; theLAO/α-olefin interpolymer is characterized by a weight average blockindex, ABI, from about 0.15 to about 0.8, (preferably from about 0.2 toabout 0.7, and more preferably from about 0.4 to about 0.6); thereinforcement material includes glass fiber (e.g., glass fibers havingan average length greater than about 0.5 mm, preferably greater thanabout 1 mm, more preferably greater than about 3 mm, and most preferablygreater than about 5 mm); the reinforcement material (e.g. the glassfiber) is present at a concentration from about 5 wt. % to about 40 wt.% (preferably from about 10 to about 40 wt. %, more preferably fromabout 15 wt. % to about 35 wt. %, and most preferably from about 20 toabout 30 wt. %, e.g., about 25 wt. %) based on the total weight of thepolymeric composition; the first polymeric component is present in theamount of about 3 wt.% to about 80 wt.% (preferably from about 10 wt. %to about 70 wt. %, more preferably from about 15 wt. % to about 50 wt.%) based on the total weight of the polymeric composition; the firstpolymer component consists essentially of one or more polypropylenes,selected from the group consisting of polypropylene homopolymer, impactpolypropylene, and random polypropylene copolymer, or any combinationthereof, wherein the polypropylene has a melting temperature greaterthan about 125° C. (preferably greater than about 140° C.) and therandom polypropylene is a copolymer of ethylene and propylene; the firstpolymer component consists essentially of isotactfc polypropylenehomopolymer; the LAO/α-olefin interpolymer is present at a concentrationfrom about 5 to about 90 wt. % (preferably from about 10 to about 60 wt.%, more preferably from about 20 to about 50 wt. %, and most preferablyfrom aohut 30 to about 45 wt. %) based on the total weight of thepolymeric composition; the first polymeric component is characterized bya melt flow rate from about 20 to about 500 g/10 min (preferably fromabout 30 to about 100, more preferably from about 50 to about 80 g/10min) as measured according to ASTM D-1238 Condition 230° C./2.16 kg; thecomposition includes a polypropylene homopolymer having a melt flow ratebetween about 30 to about 100 g/10 min as measured according to ASTMD-1238(at 230° C., 2.16 kg), a CHARPY (notched) Impact Strength betweenabout 2 and about 6 kJ/m² (preferably from about 2.2 to about 4.7 kJ/m²)as measured according to ISO 179-1/1eA (at 23° C.), or both; or thepolymeric composition is characterized by a melt flow rate of at leastabout 0.5 g/10 min (preferably at least about 2 g/10 min, and morepreferably at least about 5 g/10 min, arid most preferably at leastabout 10 g/10 min) as measured according to ASTM D-1238 Condition 230°C./2.16 kg.

Another aspect of the invention is directed at a molded article whereinthe article contains a portion having a polymeric composition asdescribed herein.

Yet another aspect of the invention is directed at a process formanufacturing a molded article wherein the molded article contains aportion having a polymeric composition as described herein, and theprocess includes a step of removing the article from a mold.

This aspect of the invention may be further characterized by one or anycombination of the following features: the process further comprises thesteps of: providing from about 3 to about 80 parts by weight (e.g., fromabout 3 to about 60 parts by weight) of a first material thai includesat least a portion of the hard thermoplastic, providing from about 10 toabout 90 (e.g., from about 10 to about 60) parts by weight of theLAC/α-olefin interpolymer having a concentration of the second α-olefinfrom about 7 to about 50 mole % (preferably from about 8 to about 40mole %, and more preferably from about 9 to about 30 mole %, and mostpreferably from about 10 about 20 mole %) based on the total weight ofthe LAO/α-olafio interpolymer, providing from about 10 to about 80 (e.g.from about 20 to about 75) parts by weight of a third material includinga reinforcement concentrate having at least a portion of the at leastone reinforcement material; blending the first, second and thirdmaterials to form a blend, and shaping the blend in a tool; the at leastone reinforcement material includes glass fibers, the third material isan admixture including at least a portion of the at least onereinforcement material and at least a portion of the relatively hardthermoplastic which includes a polypropylene; the relatively hardthermoplastic is a polyethylene (e.g., a polyethylene having a meltingtemperature greater than about 125° C. such as a polyethylenehomopolymer), a polyethylene copolymer (e.g., a low densitypolyethylene, a linear low density polyethylene, or a medium densitypolyethylene, such as one having a density greater than about 0.905g/cm³), a polypropylene homopolymer, a polypropylene impact copolymer, apolypropylene random copolymer, or any combination thereof; the at leastone reinforcement material includes long glass fibers having an averagefiber length of greater than about 5 mm; the at least one reinforcementmaterial includes short glass fibers having an average fiber length ofless than about 5 mm; the at least one relnfereernent material has anaverage fiber length of at least about 1 mm in the molded article; therelatively hard thermoplastic is present at a concentration from about 5wt. % to about 70 wt. % (preferably from about 10 wt. % to about 70 wt.%, and more preferably from about 30 wt. % to about 70 wt. %) based onthe total weight of the reinforcement concentrate; the at least onereinforcement material is present in a concentration from about 30 wt. %to about 90 wt. % (e.g. from about 35 wt. % to about 80 wt. %) based onthe total weight of the reinforcement concentrate; the at least onereinforcement material is present in the amount of about 5 wt. % toabout 40 wt. % (preferably from about 10 to about 30 wt. %, and morepreferably from about 15 to about 30 wt. %) based on total weight of themolded article; the LAO/α-olefin interpolymer is present in the amountof about 10 wt. % to about 90 wt. % (e.g. from about 10 wt. % to about60 wt. %) based on the total weight of the molded article; the processfurther comprises a step of melt compounding together two or more of thefirst material, the second material, or the third material, prior to theblending step; the process is substantially free of melt compounding anytwo of the first, second, and third materials prior to melting thematerials in the screw of the molding machine; or the process furthercomprises the steps of: melhcompoundlng the first, second, and thirdmaterials to form a melt blended polymeric composition, pelletizing themelt blended polymeric composition to form pellets or granules capableof feeding in a molding machine; and placing at least 5 kg of thepellets or granules in a container.

Another processing aspect of the invention is directed at a process forcompounding a polymeric composition as described herein, wherein theprocess comprises the steps of: melt-compounding the first polymericcomponent, the second polymeric component, and reinforcement material toform a melt blended polymeric composition; pelletizing the melt blendedpolymeric composition to form pellets or granules capable of feeding ina molding machine; and placing at least 5 kg of the pellets or granulesin a container.

DETAILED DESCRIPTION OF THE INVENTION

General Definitions

“Polymer” means a polymeric compound prepared by polymerizing monomers,whether of the same or a different type. The generic term “polymer”embraces the terms “homopolymer,” “copolymer,” “terpolymer” as well as“interpolymer.”

“Interpolymer” means a polymer prepared by the polymerization of atleast two different types of monomers. The generic term “interpolymer”includes the term “copolymer” (which is usually employed to refer to apolymer prepared from two different monomers) as well as the term“terpolymer” (which is usually employed to refer to a polymer preparedfrom three different types of monomers). It also encompasses polymersmade by polymerizing four or more types of monomers.

The term “lower-α-olefin/α-olefin interpolymer” (LAO/α-olefininterpolymer) includes “ethylene/α-olefin interpolymer” and“propylene/α-olefin interpolymer”. LAO/α-olefin interpolymer generallyrefers to polymers comprising a first α-olefin (i.e. the lower α-olefinor “LAO”) which is either ethylene or propylene and a second differentα-olefin having 3 or more carbon atoms. Without limitation theLAO/α-olefin intofpolymer may preferably contain either ethylene orpropylene and at lease one second different monomer selected from thegroup consisting of ethylene, propylene, butane, hexane, and octene.More preferably the LAO/α-olefin interpolymer is an ethylene/propyleneinterpolymer, an ethylene/butene interpolymer, an ethylene/octeneinterpolymer, a propylene/ethylene interpolymer, a propylene/buteneinterpolymer, or a propylene/octene interpolymer. Preferably, the firstα-olefin (e.g., ethylene) comprises the majority mole fraction of thewhole polymer, i.e., the LAO (e.g., ethylene) comprises at least about50 mole percent of the whole polymer. More preferably LAO (e.g.,ethylene) comprises at least about 60 mole percent, at least about 70mole percent, or at least about 80 mole percent, with the substantialremainder of the whole polymer comprising at least one other comonomerthat is preferably an α-olefin having 3 or more carbon atoms. For manyethylene/octene copolymers, the preferred composition comprises anethylene content greater than about 70 mole percent, and more preferablygreater than about 80 mole percent of the whole polymer and an octenecontent of from about 4 to about 30, preferably from about 4 to about25, mora preferably from about 10 to about 20, and most preferably fromabout 15 to about 20 mole percent of the whole polymer. In someembodiments, the LAO/α-olefin interpolymer (e.g., the ethylene/α-olefininterpolymers) do not include those produced in low yields or in a minoramount or as a by-product of a chemical process. While the LAO/α-olefininterpolymers can be blended with one or more polymers, the as-producedLAO/α-olefin interpolymers are substantially pure and often comprise amajor component of the reaction product of a polymerization process.

The LAO/α-olefin interpolymers comprise ethylene or propylene and one ormore different copolymerizable α-olefin comonomers in polymerized form,characterized by multiple blocks or segments of two or more polymerizedmonomer units differing in chemical or physical properties. That is, theLAO/α-olefin interpolymers are block interpolymers, preferablymulti-block interpolymers or copolymers. The terms “interpolymer” andcopolymer” are used interchangeably herein. In some embodiments, themulti-block copolymer can be represented by the following formula:(AB)_(n) (B(AB)_(n), or A(BA)_(n) where n is at least 1, preferably aninteger greater than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60,70, 80, 90, 100, or higher, “A” represents a hard block or segment and“B” represents a soft block or segment. Preferably, As and Bs are linkedin a substantially linear fashion, as opposed to a substantiallybranched or substantially star-shaped fashion. In other embodiments, Ablocks and B blocks are randomly distributed along the polymer chain. Inother words, the block copolymers usually do not have a structure asfollows, AAA-AA-BBB-BB

In still other embodiments, the block copolymers do not usually have athird type of block, which comprises different comonomer(s). In yetother embodiments, each of block A and block B has monomers orcomonomers substantially randomly distributed within the block. In otherwords, neither block A nor block B comprises two or more sub-segments(or sub-blocks) of distinct composition, such as a tip segment, whichhas a substantially different composition than the rest of the block.

The multi-block polymers typically comprise various amounts of “hard”and “soft” segments. “Hard” segments refer to blocks of polymerizedunits in which the first α-olefin (i.e., the ethylene or the propylene)is present in an amount greater than about 95 weight percent, andpreferably greater than about 98 weight percent based on the weight ofthe polymer. In other words, the comonomer content (content of monomersother than first α-olefin) in the hard segments is less than about 5weight percent, and preferably less than about 2 weight percent based onthe weight of the polymer. In some embodiments, the hard segmentscomprises all or substantially all ethylene. “Soft” segments, on theother hand, refer to blocks of polymerized units in which the comonomercontent (content of monomers other than the first α-olefin) is greaterthan about 5 weight percent, preferably greater than about 8 weightpercent, greater than about 10 weight percent, or greater than about 15weight percent based on the weight of the polymer. In some embodiments,the comonomer content in the soft segments can be greater than about 20weight percent, greater than about 25 weight percent, greater than about30 weight percent, greater than about 35 weight percent, greater thanabout 40 weight percent, greater than about 45 weight percent, greaterthan about 50 weight percent, or greater than about 60 weight percent.

The soft segments can often be present in a block interpolymer fromabout 1 weight percent to about 99 weight percent of the total weight ofthe block interpolymer, preferably from about 4 weight percent to about95 weight percent, from about 10 weight percent to about 95 weightpercent, from about 20 weight percent to about 95 weight percent, tornabout 40 weight percent to about 95 weight percent, from about 50 weightpercent to about 95 weight percent, from about 50 weight percent toabout 90 weight percent, from about 60 weight percent to about 90 weightpercent, from about 65 weight percent to about 90 weight, percent, orfrom about 65 weight percent to about 85 weight percent of the totalweight of the block interpolymer. Conversely, the hard segments can bepresent in similar ranges. The soft segment weight percentage and thehard segment weight percentage can be calculated based on data obtainedfrom DSC or NMR.

The term “crystalline” if employed, refers to a polymer that possesses afirst order transition or crystalline melting point (Tm) as determinedby differential scanning calorimetry (DSC) or equivalent technique. Theterm may be used interchangeably with the term “semicrystalline”. Theterm “amorphous” refers to a polymer lacking a crystalline melting pointas determined by differential scanning calorimetry (DSC) or equivalenttechnique.

The term “multi-block copolymer” or “segmented copolymer” refers to apolymer comprising two or more chemically distinct regions or segments(referred to as “blocks”) preferably joined in a linear manner, that is,a polymer comprising chemically differentiated units which are joinedend-to-end with respect to polymerized ethylenic (or propylenic)functionality, rather than in pendent or grafted fashion. In a preferredembodiment, the blocks differ in the amount or type of comonomerincorporated therein, the density, the amount of crystallinity, thecrystallite size attributable to a polymer of such composition, the typeor degree of tacticity (isotactic or syndiotactic), regio-regularity orregio-irregularity, the amount of branching, including long chainbranching or hyper-branching, the homogeneity, or any other chemical orphysical property. The multi-block copolymers are characterized byunique distributions of both polydispersity index (PDI or Mw/Mn), blocklength distribution, and/or block number distribution due to the uniqueprocess making of the copolymers. The multi-block copolymers may have aPDI from about 1.4 to about 10, preferably from about 10 to about 7,more preferably from about 2 to about 5, and most preferably from about2 to about 3.

In the following description, all numbers disclosed herein areapproximate values, regardless whether the word “about” or “approximate”is used in connection therewith. They may vary by 1 percent, 2 percent,5 percent, or, sometimes, 10 to 20 percent. Whenever a numerical rangewith a lower limit, R_(L) and an upper limit, R_(U), is disclosed, anynumber falling within the range is specifically disclosed. Inparticular, the following numbers within the range are specificallydisclosed: R=R_(L)+k*(R_(U)−R_(L)), wherein k is a variable ranging from1 percent to 100 percent with a 1 percent increment, i.e., k is 1percent, 2 percent, 3 percent, 4 percent, 5 percent, . . . , 50 percent,51 percent,. 52 percent, . . . , 95 percent 96 percent, 97 percent, 98percent, 99 percent, or 100 percent. Moreover, any numerical rangedefined by two R numbers as defined in the above is also specificallydisclosed.

In general, the present invention s directed to an improved polymericcomposition, processes of forming the composition as well as articles orparts formed of the polymeric composition, by the processes, or both.Advantageously, the polymeric composition can be employed to formsoft-touch feel parts or components with desirable characteristics atrelatively low cost, and thus finds attractive application as parts forautomotive applications (e.g., automotive interior components that aresubject to passenger contact). The polymeric composition typicallyincludes at least one hard thermoplastic (e.g. a polyolefin including atleast one polymer having greater than about 12% crystallinity selectedfrom a polypropylene homopolymer, a polyethylene homopolymer, apropylene copolymer, an ethylene copolymer, and any mixture thereof)having a relatively high crystallinity, at least one soft thermoplastic(e.g., a thermoplastic having a crystaliinity and/or hardness lower thanthe hard thermoplastic), at least one reinforcement material (e.g.,glass fibers), and optionally one or more additives that can include,without limitation, a coupling or cross-linking agent, a cross-linkingcoagent, a flame retardant, an ignition resistant additive, astabilizer, a blowing agent, a blowing agent activator, a colorant, anantioxidant a mold release agent, an anti-static agent, a slip-aid(i.e., slip resistance aid), a flow enhancer, a nucleating agent, aclarifying agent, or combinations thereof or others. In one aspect ofthe invention, the polymeric composition may be free of one or anycombination of the following: coupling-agent, cross-linking agent, orblowing agent.

It has surprisingly been shown that reinforced compositions having adesirably low hardness and/or low flexural modulus may be obtained usinga lower concentration of the relatively soft thermoplastic as comparedwith previously used soft thermoplastics. Additionally reinforcedcompositions of the present invention may have surprising improvementsin their low temperature properties (e.g., ductility at temperatures ofabout 23° C. or about −20° C.). It has unexpectedly been observed thatreinforced compositions of the present invention may also have one orany combination of the following surface properties: improved gloss,improved scratch and/or mar resistance, a more rubbery soft-touch feel,high surface friction, or elimination/reduction of tiger striping. It isalso observed that the compositions may also unexpectedly have desirablebulk properties, such as sound dampening properties, high stiffness,high heat distortion temperature and/or high Vicat softeningtemperature. These combinations of properties may allow for thereinforced compositions to be used to make a one shot molded article inapplications which currently may require at least two materials (e.g., afirst material for impartin good surface properties and a secondmaterial for imparting good bulk properties).

Additional teachings that may be applied in the practice of the presentinvention are disclosed in the concurrently filed U.S. application Ser.No. 12/256,217 filed on Oct. 22, 2008, herein incorporated by referencein its entirety. Without limitations, but by way of illustrativeexample, test methods for characterizing S/LEPs and test methods forcharacterizing propylene elastomers described in that application may beemployed herein.

Turning now in greater detail to the individual components of theoverall composition. The articles herein will typically include a firstpolymeric component that includes at least one hard thermoplastic thatis relatively strong, rigid, impact resistant, or any combinationthereof. For instance, the hard thermoplastic herein may be apolyolefinic thermoplastic including or consist essentially of one ormore olefin homopolymers or olefin copolymers. Without limitation, thefirst polymeric component may consist of high density polyethylene, lowdensity polyethylene, linear low density polyethylene, medium densitypolyethylene, isotactic polypropylene, impact polypropylene, randompolypropylene copolymer, or any combination thereof. Preferably, thehard thermoplastic includes at least one polymer selected from aisoiaefic polypropylene (e.g., a polypropylene homopolymer), impactpolypropylene, random polypropylene copolymer, or any combinationthereof. Without limitation, one specific example of a preferredpolypropylene homopolymer is disclosed in U.S. Pat. No. 7,087,680,incorporated by reference for all purposes.

A highly preferred first polymer component includes or consistsessentially of one or more isotactic polypropylene homopolymers,although other forms of polypropylene (such as impact polypropylene,random polypropylene copolymer, atactic polypropylene, and syndiptacticpolypropylene) may also be used such at low concentrations (e.g. lessthan about 35 wt %, or even less than about 10 wt % based on the totalweight of the first polymer component. Most preferably the first polymercomponent is essentially free of syndiotactic polypropylene and atacticpolypropylene). Suitable impact polypropylenes are impact polypropylenewhich are produced using a secondary copolymerization step reactingethylene with propylene and suitable random polypropylene copolymertypically contain lass than about 5 wt. % ethylene.

The first polymeric component will typically be present in an amount ofat least about 3 wt. %, preferably at least about 10 wt. %, morepreferably at least about 20 wt. % and most preferably at least about 30wt. % based on the total weight of the polymer composition. The firstpolymeric component will typically be present in an amount of less thanabout 80 wt. %, preferably less than about 75 wt. %, more preferablyless than about 55 wt. %, and most preferably less than about 45 wt. %(e.g., less than about 40 wt. %) based on the total weight of thepolymer composition.

As gleaned from this discussion, a portion of the first polymericcomponent, the second polymeric component, or both includes a portion ofthe material that is crystalline. Preferably, a portion (e.g., at least30 wt. %, preferably at least about 50 wt. %, more preferably at leastabout 70 wt. %, and most preferably at least about 95 wt. %, or evenall) of the first polymeric component has a relatively high crystalline,a portion (e.g., at least 30 wt. %, preferably at least about 50 wt. ,more preferably at least about 70 wt. %, and most preferably at leastabout 95 wt. %, or even all) of the second polymeric component has arelatively low crystalline, or both The crystalllnlty (e.g., the averagecrystallinity) of the first polymeric component may be greater thanabout 16 wt % , preferably greater than about 31 wt %, more preferablygreater than about 36 wt %, and most preferably greater than about 41 wt% (e.g., greater than about 45 wt. %). The cfystailinity of the secondpolymeric component, the soft thermoplastic, or both may be less thanthe first polymer component. For example, the second polymericcomponent, the soft thermoplastic or both may have a crystallinlty(e.g., an average crystallinity) less than about 44 wt %, preferablyless than about 40 wt %, more preferably less than about 35 wt %, andmost preferably less than about 30 wt. % (e.g., less than about 15 wt.%). The second polymer component may have a crystalliinity greater thanabout 2%, preferably greater than about 3%, more preferably greater thanabout 5%, and most preferably greater than about 7% (e.g., greater thanabout 10%) by weight. For example, the second polymer component, thesoft thermoplastic, or both may have a crystallinity from about 2% toabout 44%, preferably from about 2% to about 40%, more preferably fromabout 5% to about 35% and most preferably from about 5% to about 30%(e.g., from about 7% to about 15%) by weight.

Percent crystallinity herein can be measured by differential scanningcalorlmetry, according to ASTM D 3418.03 or ISO 11357-3. By way ofexample, a milligram size sample of polymer is sealed into an aluminumDSC pan. The sample is placed into a DSC cell with a 25 cubic centimeterper minute nitrogen purge and cooled to −100C. A standard thermalhistory is established for the sample by heating at 10° C./minute to225° C. The sample is then cooled (at 10° C./minute) to −100° C. andreheated at 10° C./minute to 225° C. The observed heat of fusion for thesecond scan is recorded (ΔH_(observed)). The observed heat of fusion isrelated to the

degree of crystallinity in weight percent based on the weight of thesample by the following equation:

${{\%\mspace{14mu}{Crystallinity}} = {\frac{\Delta\; H_{observed}}{\Delta\; H_{known}} \times 100}},$where the value for ΔH_(known) is a literature reported establishedreference value for the polymer. For example, heat of fusion forisotactic polypropylene has been reported in B. Wunderlich,Macromolecular Physics, Volume 3, Crystal Melting, Academic Press, NewYork, 1980, p. 48, is ΔH_(known)=165 Joules per gram of polypropylenepolymer; and the heat of fusion for polyethylene has been reported in F.Rodriguez, Principles of Polymer Systems, 2^(nd) Edition, HemispherePublishing Corporation, Washington, 1982, p. 54, is ΔH_(known)=287Joules per gram of polyethylene polymer. The value of ΔH_(known)=165 J/gmay be used for polymers containing greater than about 50 mole %propylene monomer and the value of ΔH_(known)=287 J/g may be used forpolymers containing greater than about 50 mole % ethylene monomers.

The molecular weight and hence the melt flow rate of the hardthermoplastic (e.g. the polypropylene) for use in the present inventionmay vary depending upon the application. In one preferred embodiment,the melt flow rate for the polypropylene useful herein is generally fromabout 0.1 grams/10 minutes (g/10 min) to about 100 g/10 min, preferablyfrom about 0.5 g/10 min to about 80 g/10 min, more preferably from about3 to about 60 g/10 min, and most preferably from about 5 g/10 min toabout 30 g/10 min measured according to ISO 1133 tested at 230° C. witha load of 2.16 kg.

As indicated, it is likely that the first polymeric component will beimportant for helping to impart rigidity, strength, and possibly evenimpact resistance to the overall resulting composition. Accordingly, thematerial selected desirably will exhibit attractive impact resistance.For example, the CHARPY (notched) impact strength (at 23° C.) for thethermoplastic polymer (e.g. the polypropylene) useful herein may begreater than about 0.8 kJ/m², preferably greater than about 1kJ/m², morepreferably greater than about 1.6 kJ/m², and most preferably greaterthan about 2 kJ/m² (e.g. greater than about 2.3 kJ/m², or even greaterthan about 4 kJ/m²) as measured according to ISO 179-1/1eA. Suitablethermoplastic polymers (e.g. suitable polypropylenes) may be also becharacterized by a CHARPY (notched) impact strength (at 23° C.) for thepolypropylene less than about 15 kJ/m², preferably less than about 12kJ/m², more preferably less than about 8 kJ/m², and most preferably lessthan about 6 kJ/m² (e.g. less than about 5 kJ/m²) as measured accordingto ISO 179-1/1eA at 23° C.

In one preferred aspect of the invention, the thermoplastic polymerincludes a polypropylene homopolymer having a melt flow rate from about1 to about 5 g/10 min as measured according to ISO 1133 (at 230° C.,2.16 kg) and a CHARPY (notched) Impact Strength from about 3 to about 8kJ/m² as measured according to ISO 179-1/1eA (at 23° C.). In a secondpreferred aspect of the invention the thermoplastic polymer includes apolypropylene homopolymer having a melt flow rate from about 40 to about60 g/10 min (e.g., from about 50 to about 55 g/10 min) as measuredaccording to ISO 1133 (at 230° C., 2.16 kg) and a CHARPY (notched)Impact Strength from about 1 to about 5 kJ/m² as measured according toISO 179-1/1 eA (at 23° C.). In a third preferred aspect of the inventionthe thermoplastic polymer includes a polypropylene impact copolymerhaving a melt flow rate from about 30 to about 55 g/10 min (e.g., fromabout 37 to about 47 g/10 min) as measured according to ISO 1133 (at230° C., 2.16 kg) and a CHARPY (notched) Impact Strength from about 4 toabout 12 kJ/m² (e.g., from about 5 to about 8 kJ/m²) as measuredaccording to ISO 179-1/1eA (at 23° C.).

It is appreciated that the first polymeric component (e.g., the one ormore hard thermoplastics) useful herein may exhibit a Flexural Modulusas measured according to ISO 178 that typically ranges from about 1400to about 1800 MPa, and more specifically from about 1500 to about 1700MPa; a Tensile Strength at Yield according to ISO 527-2 that typicallyranges from about 20 to about 50 MPa, and more specifically from about30 to about 40 MPa; a Tensile Elongation at Yield according to ISO 527-2that ranges from about 5 to about 20%, more specifically from about 7 toabout 15%, or any combination thereof. In one highly preferredembodiment, the first polymeric component includes a propylene polymer,preferably a polypropylene homopolymer, and most preferably an isotacticpolypropylene (e.g., an isotactic polypropylene which contains less thanabout 5 wt % atactic polypropylene). Although, it may nonethelessinclude a random copolymer or even an impact copolymer (which alreadycontains a rubber phase). Examples of particularly preferredpolypropylene homopolymrs for use herein include one or both H705-03 orH734-52, available from The Dow Chemical Company or others havingsimilar characteristics. Examples of particularly preferredpolypropylene impact copolymers for use herein include C705-44NA,available from The Dow Chemical Company or others having similarcharacteristics.

Second Polymeric Component

The second polymeric component is characterized in being softer (e.g.,low Shore A durometer), more flexible (e.g., lower flexural modulus), orlower crystallinity than the hard first polymeric component The secondpolymeric component typically includes one or more soft thermoplastics.Suitable soft thermoplastics include an olefinic block copolymer (e.g.,an ethylene/α-olefin interpolymer), a substantially linear or linearethylene polymer (“S/LEP”), a polypropylene elastomer, or anycombination thereof. Preferably the second polymer component includes orconsists essentially of an ethylene/α-olefin interpolymer.

Olefinic block polymer/ethylene/α-olefin interpolymer

In one aspect of the invention, the second polymeric component mayinclude an multi-block polymer having a plurality of blocks, including ahard block having a relatively high crystallinity and a soft blockhaving a crystallinity lower than the hard block. The multi-blockpolymer (e.g., the multi-block olefenic polymer) may be a homopolymerincluding essentially one (e.g., one) α-olefin monomer or copolymerincluding two α-olefin monomers a terpolymer including three or moremonomers (which typically contain at least two monomers that are olefinsand may even contain three α-olefins) or may contain four or more ofα-olefin monomers. A multi-block homopolymer may contain hard and softblocks having the same monomer, the differences in the blocks being theregularity of the monomers (e.g., the hard block may have monomers whichare more regularly oriented than the soft block, so that the hard blockhas a higher crystallinity). An olefinlc block copolymer may containblocks having different concentrations of monomers. For example, anolefinic block copolymer may have one or more hard blocks which containsa high concentration (e.g., greater than about 80 wt. %, preferablygreater than about 90 wt. %, more preferably greater than about 95 wt.%, and most preferably greater than about 99 wt. %, or even 100 wt. % ofthe olefinlc block copolymer) of a first α-olefinic monomer and a lowconcentration of a second α-olefin monomer and one or more soft blockswhich contain a concentration of the first α-olefin which is lower thanthe in the one or more hard blocks. Without limitation, the olefinicblock copolymer may be an ethylene/α-olefin interpolymer. Examples ofethylene/α-olefin interpolymer which may be used in the second polymericcomponent are described in PCT international Patent Publication Nos.WO2006/102155A2 (filed Mar. 15, 2006), WO2006/101966A1 (filed Mar. 15,2006), WO2006101932A2 (filed Mar. 15, 2006), and WO2006102155A2 (filedMar. 15, 2006), all of which are expressly incorporated herein byreference in there entirety.

Ethylene/α-Olefin Interpolymers

Ethylene/α-olefin interpolymers suitable for use in the second polymericcomponent include ethylene and one or more copolymerizable α-olefincomonomers in polymerized form, characterized by multiple blocks orsegments of two or more polymerized monomer units differing in chemicalor physical properties (block interpolymer), preferably a multi-blockcopolymer.

Suitable ethylene/α-olefin interpolymers block interpolymers may have amolecular fraction which elutes between 40° C. and 130° C., whanfractionated using TREF increments, characterized in that every fractionthat has an ATREF elutlon temperature between 40° C. and less than about76° C., has a melt enthalpy (heat of fusion) as measured by DSC,corresponding to the equation: Heat of fusion (J/gm)≦(1.1312) (ATREFelutlon temperature in Celsius)+22.97.

Average Block Index

Suitable ethylene/α-olefin interpolymer may be characterized by anaverage block index, ABI, which is greater than zero and up to about 1.0and a molecular weight distribution, Mw/Mn, greater than about 1.3. Theaverage block index, ABI, is the weight average of the block index(“BI”) for each of the polymer fractions obtained in preparative TREFfrom 20° C. and 110° C., with an increment of 5° C.: ABI=Σw_(i)BI_(j))where BI_(j) is the block index for the ith fraction of the inventiveethylene/α-olefin interpolymer obtained in preparative TREF, and w_(i)is the weight percentage of the ith fraction.

For each polymer fraction, BI is defined by one of the two followingequations (both of which give the same BI value):BI=[(1/T _(X))−(1/T _(XO))]/[(1/T _(A))−(1/T _(AB))], orBI=−[LnP _(X) −LnP _(XO)]/[LnP _(A) −LnP _(AB)]

where T_(X) is the preparative ATREF elution temperature for the ithfraction (preferably expressed in Kelvin), P_(X) is the ethylene molefraction for the which fraction, which can be measured by NMR or IR asdescribe below. P_(AB) is the ethylene mole fraction of the wholeethylene/α-olefin interpolymer (before fractionation), which also can bemeasured by NMR or IR. T_(A) and P_(A) are the ATREF elution temperatureand the ethylene mole fraction for pure “hard segments” (which refer tothe crystalline segments of the interpolymer). As a first orderapproximation, the T_(A) and P_(A) values are set to those for highdensity polyethylene homopolymer, if the actual values for the “hardsegments” are not available. For calculations performed herein, T_(A) is372.degree. K., P_(A) is 1.

T_(AB) is the ATREF temperature for a random copolymer of the samecomposition and having an ethylene mole fraction of P_(AB) T_(AB) can becalculated from the following equation: LnP_(AB)=α/T_(AB)+β where α andβ are two constants which can be determined by calibration using anumber of known random ethylene copolymers. It should be noted that aand β may vary from instrument to instrument. Moreover, one would needto create their own calibration curve with the polymer composition ofinterest and also in a similar molecular weight range as the fractions.There is a slight molecular weight effect. If the calibration curve isobtained from similar molecular weight ranges, such effect would beessentially negligible. In some embodiments, random ethylene copolymerssatisfy the following relationship:LnP=−237.83/T _(ATREF)+0.639T_(XO) is the ATREF temperature for a random copolymer of the samecomposition and having an ethylene mole fraction of P_(X). T_(XO) can becalculated from LnP_(X)=α/T_(X)+β. Conversely, P_(XO) is the ethylenemole fraction for a random copolymer of the same composition and havingan ATREF temperature of T_(X), which can be calculated fromLnP_(X)=α/T_(XO)+β.

Once the block index (BI) for each preparative TREF fraction isobtained, the weight average block index, ABI, for the whole polymer canbe calculated. In one class of suitable ethylene/α-olefin interpolymers,ABI may be greater than zero but less than about 0.15 or from about 0.1to about 0.3. In another class of suitable ethylene/α-olefininterpolymers, ABI may be greater than about 0.15, preferably greaterthan about 0.2, more preferably greater than about 0.3 and mostpreferably greater than about 0.4. Such materials may also becharacterized by an ABI less than about 0.9, preferably less than about0.8, more preferably less than about 0.7 and most preferably less thanabout 0.6.

ATREF Peak Comonomer Composition Measurement by Infra-Red Detector

The comonomer composition of the TREF peak can be measured using an IR4infra-red detector available from Polymer Char, Valencia, Spain(http:/www.polymerchar.com).

The “composition mode” of the detector is equipped with a measurementsensor (CH₂) and composition sensor (CH₃) that are fixed narrow bandinfra-red filters in the region of 2800-3000 cm.sup.-1. The measurementsensor detects the methylene (CH₂) carbons on the polymer (whichdirectly relates to the polymer concentration in solution) while thecomposition sensor detects the methyl (CH₃) groups of the polymer. Themathematical ratio of the composition signal (CH₃) divided by themeasurement signal (CH₂) is sensitive to the comonomer content of themeasured polymer in solution and its response is calibrated with knownethylene alpha-olefin copolymer standards.

The detector when used with an ATREF instrument provides both aconcentration (CH₂) and composition (CH₃) signal response of the elutedpolymer during the TREF process. A polymer specific calibration can becreated by measuring the area ratio of the CH₃ to CH₂ for polymers withknown comonomer content (preferably measured by NMR). The comonomercontent of an ATREF peak of a polymer can be estimated by applying a thereference calibration of the ratio of the areas for the individual CH₃and CH₂ response (i.e. area ratio CH₃/CH₂ versus comonomer content).

The area of the peaks can be calculated using a full width/half maximum(FWHW) calculation after applying the appropriate baselines to integratethe individual signal responses from the TREF chromatogram. The fullwidth/half maximum calculation is based on the ratio of methyl tomethylene response area [CH₃/CH₂] from the ATREF infra-red detector,wherein the tallest (highest) peak is identified from the base line, andthen the FWHM area is determined. For a distribution measured using anATREF peak, the FWHM area is defined as the area under the curve betweenT1 and T2, where T1 and T2 are points determined, to the left and rightof the ATREF peak, by dividing the peak height by two, and then drawinga line horizontal to the base line, that intersects the left and rightportions of the ATREF curve.

The application of infra-red spectroscopy to measure the comonomercontent of polymers in this ATREF-infra-red method is, in principle,similar to that of GPC/FTIR systems as described in the followingreferences: Markovich, Ronald P.; Hazlitt, Lonnie G.; Smith, Linley;“Development of gel-permeation chromatography-Fourier transform infraredspectroscopy for characterization of ethylene-based polyolefincopolymers”. Polymeric Materials Science and Engineering (1991), 65,98-100; and Deslauriers, P. J.; Rohlfing, D. C.; Shieh, E. T.;“Quantifying short chain branching miorostrcetures in ethylene-1-olefincopolymers using size exclusion chromatography and Fourier transforminfrared spectroscopy (SEC-FTIR)”, Polymer (2002), 43, 59-170, both ofwhich are incorporated by reference herein in their entirety.

Relationship between Melting Point and Density

LAO/α-olefin Interpolymers (e.g., ethylene/α-olefin interpolymers)suitable for use in the polymeric composition of the invention may becharacterized by a melting point, Tm, which is higher than the meltingpoint of a random copolymer having the same density, d. For example, theLAO/α-olefin interpolymers (e.g., the ethylene/α-olefin interpolymers)may have at least one melting point, Tm, in degrees Celsius and density,d, in grams/cubic centimeter, wherein the numerical values of thevariables correspond to the relationship: Tm≧1000(d)-790, and preferablyTm>−2002.9+4538(d)−2422.2(d)², more preferablyTm≧6288.1+13141(d)−6720.3(d)², and most preferablyTm≧858.91−1825.3(d)+1112.8(d)².

Preferably, the LAO/α-olefin interpolymers (e.g., the ethylene/α-olefininterpolymers) suitable for use in the polymeric composition of theinvention have a Mw/Mn from about 1.7 to about 3.5 and at least onemelting point, Tm, in degrees Celsius and density, d, in grams/cubiccentimeter, wherein d≦0.900, and the numerical values of the variablescorrespond to the relationship: Tm≧1000(d)−790, and preferablyTm>-2002.9+4538.5(d)−2422.2(d)², more preferablyTm≧6288.1+13141(d)−6720.3(d)², and most preferablyTm≧858.91−1825.3(d)+1112.8(d)².

Relationship Between the Heat of Fusion and the Difference Between theTallest DSC Peak and the Tallest CRYSTAF Peak

Suitable LAO/α-olefin interpolymers (e.g., suitable ethylene/α-olefininterpolymers) may be characterized by a difference between the tallestDifferential Scanning Calorimatry (“DSC”) peak minus the temperature ofthe tallest Crystallization Analysis Fractionation (“CRYSTAF”) peakwhich is higher than for a random copolymer having the same heat offusion. For example, suitable LAO/α-olefin interpolymers (e.g.,ethylene/α-olefin interpolymers) may comprise, in polymerized form,ethylene or propylene and one or more different α-olefins and arecharacterized by a ΔT, in degree Celsius, defined as the temperature forthe tallest DSC peak minus the temperature for the tallest CRYSTAF peakand a heat of fusion in J/g, ΔH, and ΔT and ΔH which may satisfy thefollowing relationships: ΔT≧−0.1299(ΔH)+62,81, and preferablyΔT≧0.1299(ΔH)+64.38, and more preferably ΔT≧−0.1299(ΔH) +65.95, for ΔHup fo 130 J/g. Moreover, ΔT may be equal to or greater than 48° C. forΔH greater than 130 J/g. The CRYSTAF peak is determined using at least 5percent of the cumulative polymer (that is, the peak must represent atleast 5 percent of the cumulative polymer), and if less than 5 percentof the polymer has an identifiable CRYSTAF peak, then the CRYSTAFtemperature is 30° C., and ΔH is the numerical value of the heat offusion in J/g. More preferably, the highest CRYSTAF peak contains atleast 10 percent of the cumulative polymer.

Relationship Between the Elastic Recovery and the Density

Suitable LAO/α-olefin interpolymers (e.g., suitable ethylene/α-olefininterpolymers) may have an elastic recovery, Re, in percent at 300percent strain and 1 cycle measured on a compression-molded film of theinterpolymer which is higher than the elastic recovery of a randomcopolymer having the same density. For example, suitable LAO/α-olefininterpolymers (e.g., ethylene/α-olefin interpolymers) may becharacterized by an elastic recovery, Re, and a density, d, in g/cm³,wherein the numerical values of Re and d may satisfy the followingrelationship when the interpolymer is substantially free of across-linked phase: Re>1481−1629(d); and preferably Re≧1491−1629(d): andmore preferably Re≧1501−1629(d); and even more preferablyRe≧1511−1629(d).

Molar Comonomer Concentration of TREF Fractions

Suitable LAO/α-olefin interpolymers (e.g., suitable ethylene/α-olefininterpolymers) when fractionated using Temperature Rising ButtonFractionation (“TREF”), may have at least fraction which has arelatively high molar comonomer concentration, (i.e., the interpolymermay have a molar comonomer concentration which is higher than forfraction of a compositionally similar random copolymer which is elutedat the same temperature). For example, the LAO/α-olefin interpolymers(e.g., the ethylene/α-olefin interpolymers) may have a molecularfraction which elutes between 40° C. and 130° C. when fractionated usingTREF, which may be characterized in that said fraction has a molarcomonomer content higher, preferably at least 5 percent higher, morepreferably at least 10, 15, 20 or 25 percent higher, than that of acomparable random ethylene interpolymer fraction elutiog between thesame temperatures, wherein said comparable random copolymer comprisesthe same comonomer(s), preferably it is the same comonomer(s), and amelt index, density, and molar comonomer content (based on the wholepolymer) within 10 percent of that of the blocked interpolymer.Preferably, the Mw/Mn of the comparable copolymer is also within 10percent of that of the blocked interpolymer and/or the comparablecopolymer has a total comonomer content within 10 weight percent of thatof the blocked interpolymer.

Comonomers and Concentration

The LAO/α-olefin interpolymers (e.g., the ethylene/α-olefininterpolymers) used in the polymer compositions of the invention arepreferably interpolymers of ethylene or propylene with at least onedifferent C₃-C₂₀ α-olefin. Copolymers of ethylene and a C₃-C₁₂ α-olefinare especially preferred. The interpolymers may further comprise C₄-C₁₈diolefin and/or alkenylbenzene. Suitable unsaturated comonomers usefulfor polymerizing with ethylene include, for example, ethylenicallyunsaturated monomers, conjugated or nonconjugated dienes, polyenes,alkenylbenzenes, etc. Examples of such comonomers include C.sub.3-C₂₀α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene,4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and thelike. 1-Butene and 1-octene are especially preferred. Other suitablemonomers include styrene, halo- or alkyl-substituted styrenes,vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and naphthenics(e.g., cyclopentene, cyclohexene and cyclooctene).

While ethylene/α-olefin interpolymers are preferred polymers, otherethylene/olefin polymers may also be used. Olefins as used herein referto a family of unsaturated hydrocarbon-based compounds with at least onecarbon-carbon double bond. Depending on the selection of catalysts, anyolefin may be used in embodiments of the invention. Preferably, suitableolefins are C₂-C₂₀ aliphatic and aromatic compounds containing vinylicunsaturation, as well as cyclic compounds, such as cyclobutene,eyclopentene, dicyclopentadiene, and norbornene, including but notlimited to, norbonene substituted in the 5 and 6 position with C₁-C₂₀hydrocarbyl or cyclobydrocarbyl groups. Also included are mixtures ofsuch olefins as well as mixtures of such olefins with C₄-C₄₀ diolefincompounds.

Examples of olefin monomers include, but are not limited to propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, and 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, 1-eicosene, 3-methyl-1-butane, 3-methyl-1-pentene,4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4-vinylcyclohexene,vinylcyclohexane, norbomadiene, ethylidene norbomene, cyclopentene,cyclohexene, dicyclopentadiene, cyclooctane, C₄-C₄₀ dienes, includingbut not limited to 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene,1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other C₄-C₄₀ α-olefins, andthe like. In certain embodiments, the α-olefin is propylene, 1-butane,1-pentene, 1-hexene, 1-octene or a combination thereof. Although anyhydrocarbon containing a vinyl group potentially may be used inembodiments of the invention, practical issues such as monomeravailability, cost, and the ability to conveniently remove unreactedmonomer from the resulting polymer may become more problematic as themolecular weight of the monomer becomes too high.

The polymerization processes described herein are well suited for theproduction of olefin polymers comprising monovinylidiene aromaticmonomers including styrene, α-methyl styrene, p-methyl styrene,t-butylstyrene, and the like. In particular, interpolymers comprisingethylene and styrene can be prepared by following the teachings herein.Optionally, copolymers comprising ethylene, styrene and a C₃-C₂₀ alphaolefin, optionally comprising a C₄-C₂₀ diene, having improved propertiescan be prepared.

Suitable non-conjugated diene monomers can be a straight chain, branchedchain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms.Examples of suitable non-conjugated dienes include, but are not limitedto, straight chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadlene,1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene;3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene anddihydroocinene, single ring alicyclic dienes, such as1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and1,5-cyclododecadiene, and multi-ring alicyclic fused and bridged ringdienes, such as tetrahydroindene, methyl tetrahydroindene,dicyclopentadiene, bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene,cycloalkenyl and cyctoalkylidene norbornenes, such as5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene,5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene,5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbomadiene.Of the dienes typically used to prepare EPOMs, the particularlypreferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene(ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB),and dicyclopentadiene (DCPD). The especially preferred dienes are5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

The LAO/α-olefin interpolymers (e.g., the ethylene/α-olefininterpolymers) may be an interpolymer including an first α-olefin(either ethylene or propylene) and a second different α-olefin (e.g.,butane, or octane) having a second α-olefin concentration (e.g., abutene concentration, or an octane concentration) greater than about 6mole %, preferably greater than about 8 mole %, more preferably greaterthan about 9 mole %, and most preferably greater than about 10 mole %based on the monomers of the interpolymer. The interpolymer may have asecond α-olefin concentration (e.g., an octane concentration, or abutane concentration) less than about 40 mole %, preferably less thanabout 30 mole %, mom preferably less than about 25 mole %, and mostpreferably less than about 20 mole % based on the monomers of theinterpolymer.

The LAO/α-olefin interpolymers (e.g., the ethylene/α-olefininterpolymers) may be an interpolymer including an first α-olefin(either ethylene or propylene) and a second different α-olefin (e.g.,butane, or octane) having a first α-olefin concentration (e.g., anethylene concentration, or a propylene concentration) greater than about20 wt. %, preferably greater than about 40 wt. %, more preferablygreater than about 60 wt., %, and most preferably greater than about 70wt. % based on the total weight of the interpolymer. The interpolymermay have a first α-olefin concentration (e.g., an ethyleneconcentration, or a propylene concentration) less than about 95 wt. %,preferably less thm about 90 wt. %, more preferably less than about 85wt. %, and most preferably less than about 80 wt. % based on the totalweight of the interpolymer.

The LAO/α-olefin interpolymers (e.g., ethylene/α-olefin interpolymers)may be an interpolymer including an ethylene or a propylene and a seconddifferent α-olefin (e.g., butene, or octene) wherein the totalconcentration of the ethylene or propylene and second α-olefin isgreater than about 90 wt. %, preferably greater than about 95 wt. %,more preferably greater than about 98 wt. %, and most preferably greaterthan about 99 wt. % (e.g., about 100 wt. %) based on the total weight ofthe interpolymer.

Density

Suitable LAO/α-olefin interpolymers (e.g., ethylene/α-olefininterpolymers) may be characterized by a density greater than about0.850, preferably greater than about 0.855, more preferably greater thanabout 0.860, and most preferably greater than about 0.885 g/cm³.Suitable ethylene/α-olefin interpolymers may be characterized by adensity less than about 0.900, preferably less than about 0.895, morepreferably less than about 0.890, and most preferably less than about0.888 g/cm³.

Hardness

The LAO/α-olefin interpolymers (e.g., the ethylene/α-olefininterpolymers) may be characterized by a Shore A hardness greater thanabout 15, preferably greater than about 40, more preferably greater thanabout 55, and most preferably greater than about 70. Theethylene/α-olefin interpolymer may be characterized by a Shore Ahardness less than about 95, preferably less than about 90, and morepreferably less than about 85. For example, the Shore A hardness may befrom about 15 to about 95, preferably from about 40 to about 90, evenmore preferably from about 70 to about 90.

Melt Index ratio

The LAO/α-olefin interpolymers (e.g., the ethylene/α-olefininterpolymers) may be characterized by a melt index ratio, I₁₀/I₂,greater than about 5, preferably greater than about 5.5, more preferablygreater than about 6, and most preferably greater than about 6,3. TheLAO/α-olefn interpolymers (e.g., the ethylene/α-olefin interpolymers)may be characterized by a melt index ratio, I₁₀/I₂, less than about 35,preferably lass than about 25, more preferably less than about 14, andmost preferably less than about 10.

Melt Index

The LAO/α-olefin interpolymers (e.g., the ethylene/α-olefininterpolymers)r may be characterized by a melt index, I₂, greater thanabout 0.2, preferably greater than about 0.5, and most preferably atleast about 1. The LAO/α-olefin interpolymers (e.g., theethylene/α-olefin interpolymers) may be characterized by a melt index,I₂, less than about 40, preferably less than about 20, and mostpreferably less than about 10.

Polydispersity Index

The LAO/α-olefin interpolymers (e.g., the ethylene/α-olefininterpolymers) may be characterized by a polydispersity index, Mw/Mn,defined by the ratio of the weight average molecular weight, Mw, and thenumber average molecular weight, Mn, greater than about 1.7, preferablygreater than about 1.9, more preferably at least about 2. TheLAO/α-olefin interpolymers (e.g., the ethylene/α-olefin interpolymers)may be characterized by a polydispersity index less than about 7,preferably less than about 5, more preferably less than about 3.5 andmost preferably less than about 3.

Sot Blocks

The LAO/α-olefin interpolymers (e.g., the ethylene/α-olefininterpolymers) may be characterized by a concentration of soft hlockCs)from about 40 to about 95 wt. % (preferably from about 50 to about 95wt. %, and more preferably from about 60 to about 90 wt. %) based on thetotal weight of the interpolymer.

Test Methods for the LAO/α-Olefin Interpolymers

Standard CRYSTAF Method

Branching distributions (e.g., comonomer distributions) may determinedby crystallization analysis fractionation (CRYSTAF) using a CRYSTAF 200unit commercially available from PolymerChar, Valencia, Spain. Thesamples are dissolved in 1,2,4 trichlorobenzene at 160° C. (0.66 mg/mL)for 1 hr and stabilized at 95° C. for 45 minutes. The samplingtemperatures range from 95 to 30° C. at a cooling rate of 0.2° C./min.An infrared detector is used to measure the polymer solutionconcentrations. The cumulative soluble concentration is measured as thepolymer crystallizes while the temperature is decreased. The analyticalderivative of the cumulative profile reflects the short chain branchingdistribution of the polymer.

The CRYSTAF peak temperature and area are identified by the peakanalysis module included in the CRYSTAF Software (Version 2001.b,PolymerChar, Valencia, Spain). The CRYSTAF peak finding routineidentifies a peak temperature as a maximum in the dW/dT curve and thearea between the largest positive inflections on either side of theidentified peak in the derivative curve. To calculate the CRYSTAF curve,the preferred processing parameters are with a temperature limit of 70°C. and with smoothing parameters above the temperature limit of 0.1, andbelow the temperature limit of 0.3.

DSC Standard Method

Differential Scanning Calorimetry analysis of the ethylene/α-olefininterpolymer may be determined using a TAI model Q1000 DSC equipped withan RCS cooling accessory and an autosampler. A nitrogen purge gas flewof 50 ml/min is used. The sample is pressed into a thin film and meltedin the press at about 175° C. and then air-cooled to room temperature(25° C.). 3-10 mg of material is then cut into a 6 mm diameter disk,accurately weighed, placed in a light aluminum pan (ca 50 mg), and thencrimped shut. The thermal behavior of the sample is investigated withthe following temperature profile. The sample is rapidly heated to 180°C.and held isothermal for 3 minutes in order to remove any previousthermal history. The sample is then cooled to −40° C. at 10° C./mincooling rate and held at −40° C. for 3 minutes. The sample is thenheated to 150° C. at 10° C./min. heating rate. The cooling and secondheating curves are recorded.

The DSC melting peak is measured as the maximum in heat flow rate (W/g)with respect to the linear baseline drawn between −30° C. and end ofmelting. The heat of fusion is measured as the area under the meltingcurve between −30° C. and the end of melting using a linear baseline.

GPC Method

The gel permeation chromatographic system consists of either a PolymerLaboratories Model PL-210 or a Polymer Laboratories Model PL-220instrument. The column and carousel compartments are operated at 140° C.Three Polymer Laboratories 10-micron Mixed-B columns are used. Thesolvent is 1,2,4 trichlorobenzene. The samples are prepared at aconcentration of 0.1 grams of polymer in 50 milliliters of solventcontaining 200 ppm of butylated hydroxytoluene (BHT). Samples areprepared by agitating lightly for 2 hours at 160° C. The injectionvolume used is 100 microliters and the flow rate is 1.0 ml/minute.

Calibration of the GPC column set is performed with 21 narrow molecularweight distribution polystyrene standards with molecular weights rangingfrom 580 to 8,400,000, arranged in 6 “cocktail” mixtures with at least adecade of separation between individual molecular weights. The standardsare purchased from Polymer Laboratories (Shropshire, UK). Thepolystyrene standards are prepared at 0.025 grams in 50 milliliters ofsolvent for molecular weights equal to or greater than 1,000,000, and0.05 grams in 50 milliliters of solvent for molecular weights less than1,000,000. The polystyrene standards are dissolved at 80° C. with gentleagitation for 30 minutes. The narrow standards mixtures are run firstand in order of decreasing highest molecular weight component tominimize degradation. The polystyrene standard peak molecular weightsare converted to polyethylene molecular weights using the followingequation (as described in Williams and Ward, J. Polym. Sci. Polym. Let.6, 621 (1968)): M_(polyethylene)=0.4316(M_(polysytrene)).

Polyethylene equivalent molecular weight calculations may be performedusing Viscotek TriSEC software Version 3.0.

Density

Samples for density measurement may be prepared according to ASTM D1928. Measurements are made within one hour of sample pressing usingASTM D792, Method B.

Flexural/Secant Modulus/Storage Modulus

Samples are compression molded using ASTM D1928. Flexural and 2 percentsecant moduli are measured according to ASTM D-790. Storage modulus ismeasured according to ASTM D 5026-01 or equivalent technique.

Mechanical Properties—Tensile, Hysteresis, and Tear

Stress-strain behavior in uniaxial tension may be measured using ASTM D1708 micro-tensile specimens. Samples are stretched with an Instron at500% min.sup.-1 at 21° C. Tensile strength and elongation at break arereported from an average of 5 specimens.

100% and 300% Hysteresis may be determined from cyclic loading to 100%and 300% strains using ASTM D 1708 microtensile specimens with anInstruct instrument. The sample is loaded and unloaded at 267% min⁻¹ for3 cycles at 21° C. Cyclic experiments at 300% and 80° C. are conductedusing en environmental chamber. In the 80° C. experiment, the sample isallowed to equilibrate for 45 minutes at the test temperature beforetesting. In the 21° C., 300% strain cyclic experiment, the retractivestress at 150% strain from the first unloading cycle is recorded.Percent recovery for all experiments are calculated from the firstunloading cycle using the strain at which the load returned to the baseline. The percent recovery, Re, is defined as:Re=100×(ε_(f)−ε_(s))/ε_(f)where ε_(f) is the strain taken for cyclic loading and ε_(s) is thestrain where the load returns to the baseline during the 1^(st)unloading cycle.Melt Index

When the LAO/α-oleftn interpolymer is an ethylene/α-olefin interpolymer,I₂, is measured in accordance with ASTM D 1238, Condition 190° C./2.16kg and I₁₀ is also measured in accordance with ASTM D 1238, Condition190° C./10 kg. When the LAO/α-olefin interpolymer is anpropylene/α-olefin interpolymer, I₂, is measured in accordance with ASTMD 1238, Condition 230° C./2.16 kg and I₁₀ is also measured in accordancewith ASTM D 1238, Condition 230° C./10 kg.

ATREF

Analytical temperature rising eiutlon fractionation (ATREF) analysis isconducted according to the method described in U.S. Pat. No. 4,798,081and Wilde, L.; Ryle, T. R.; Knobeloch, D. C.; Peat, I. R.; Determinationof Branching Distributions in Polyethylene and Ethylene Copolymers, J.Polym. Sci., 20, 441-455 (1982), which are incorporated by referenceherein in their entirety. The composition to be analyzed is dissolved intirichlorobenzene and allowed to crystallize in a column containing aninert support (stainless steel shot) by slowly reducing the temperatureto 20° C. at a cooling rate of 0.1° C./min. The column is equipped withan infrared detector. An ATREF chromatogram curve is then generated byeluting the crystallized polymer sample from the column by slowlyincreasing the temperature of the eluting solvent (trichlorobenzene)from 20 to 120° C. at a rate of 1.5° C./min.

¹³C NMR Analysis

The MMR samples may be prepared by adding approximately 3 g of a 50/50mixture of tetrachloroethane-d,sup.2/orthodichlorobenzene to 0.4 gsample in a 10 mm NMR tuoe. The samples are dissolved and homogenized byheating the tube and its contents to 150° C. The data are collectedusing a JEOL Eclipse™ 400 MHz spectrometer or a Vanan Unity Plus™ 400MHz spectrometer, corresponding to a .sup.13C resonance frequency of100.5 MHz. The data are acquired using 4000 transients per data filewild a 6 second pulse repetition delay. To achieve minimumsignal-to-noise for quantitative analysis, multiple data flies are addedtogether. The spectral width is 25,000 Hz with a minimum file state of32K data points. The samples are analyzed at 130° C. in a 10 mm broadband probe. The comonomer incorporation is determined using Randall'striad method (Randall, J. C.; JMS-Rev. Macromol. Chem. Phys., C29,201-317 (1989), which is incorporated by reference herein in itsentirety.

Polymer Fractionation by TREF

Large-scale TREF fractionation may be earned by dissolving 15-20 g ofpolymer in 2 liters of 1,2,4-trichlorobenzene (TCB) by stirring for 4hours at 160° C. The polymer solution is forced by 15 psig (100 kPa)nitrogen onto a 3 inch by 4 foot (7.6 cm.times.12 cm) steel columnpacked with a 60:40 (v:v) mm of 30-40 mesh (600-425 μm) spherical,technical quality glass beads (available from Potters Industries, HC 30Box 20, Brownwood, Tex., 76801) and stainless steel, 0.028″ (0.7 mm)diameter cut wire shot (available from Pellets, Inc. 63 IndustrialDrive, North Tonawanda, N.Y., 14120). The column is immersed in athermally controlled oil jacket, set initially to 160°C. The column isfirst cooled ballistically to 125° C., then slow cooled to 20° C. at0.04° C. per minute and held for one hour. Fresh TCB is introduced atabout 65 ml/min while the temperature is increased at 0.167° C. perminute.

Approximately 2000 ml portions of eluant from the preparative TREFcolumn are collected in a 16 station, heated fraction collector. Thepolymer is concentrated in each fraction using a rotary evaporator untilabout 50 to 100 ml of the polymer solution remains. The concentratedsolutions are allowed to stand overnight before adding excess methanol,filtering, and rinsing (approx. 300-500 ml of methanol including thefinal rinse). The filtration step is performed on a 3 position vacuumassisted filtering station using 5.0 μm polytetrafluoroethylene coatedfilter paper (available from Osmonics Inc., Cat# Z50WP04750). Thefiltrated fractions are dried overnight in a vacuum oven at 60° C. andweighed on an analytical balance before further testing.

The second polymeric component (which may comprise or consist of one ormore LAO/α-olefin interpolymers, such as ethylene/α-olefin interpolymersor a propylene/α-olefin interpolymers) may be present in the polymercomposition at a concentration greater than about 10 wt. %, preferablygreater than about 15 wt. %, more preferably greater than about 20 wt.%, and most preferably greater than about 25 wt. % (e.g., greater thanabout 35 wt. %) based on the total concentration of the first polymericcomponent and the second polymeric component. The second polymercomponent (e.g., the ethylene/α-olefin interpolymer, or thepropylene/α-olefin interpolymer) may be present in the polymercomposition at a concentration less than about 70 wt. %, preferably lessthan about 60 wt. %, more preferably less than about 55 wt. %, and mostpreferably less than about 50 wt. % (e.g., even less than about 45 wt.%) based on the total concentration of the first polymeric component andthe second polymeric component.

Propylene Containing Elastomer

The second polymeric component may also include or consist essentiallyof a polypropylene elastomer. Suitable polypropylene elastomers maycontain propylene monomer at a concentration greater than about 50 wt.%, preferably greater than about 65 wt. %, more preferably greater thanabout 70 wt. %, and most preferably greater than about 80 wt. % (e.g.,at least 85 wt. %) based on the weight of the polypropylene elastomer.The polypropylene elastomer may also contain one or more additionalC₂₋₁₂ α-olefin comonomers (e.g., a comonomer including ethylene, orconsisting of ethylene, or including butene, or consisting of butene) ata concentration greater than about 5 wt. %, preferably greater thanabout 7 wt. %, more preferably greater than about 9 wt. %, and mostpreferably greater than about 12 wt. % based on the total weight of thepolypropylene elastomer. For example, the comonomer content may rangefrom about 5 to about 40 percent by weight of the polypropyleneelastomer composition, more preferably from about 7 to about 30 percentby weight of the polypropylene elastomer composition, and still morepreferably from about 9 to about 15 percent by weight of thepolypropylene elastomer composition. The polypropylene elastomer mayhave some crysfaiiioify or may be amorphous. Suitable polypropyleneelastomers may have a peak melting temperature less than about 130° C.preferably less than about 115° C., and most preferably less than about100° C., as measured by differential scanning calorimetry at a heatingrate of about 10° C./minn on a sample which has been cooled from about220° C. to about 0° C. at a rate of about 10° C./min.

The propylene elastomer preferably contains an α-olefin selected fromethylene, butene, hexene, and octane. More preferably the propyleneelastomer contains an α-olefin selected from ethylene, butene, andoctane. Most preferably the propylene elastomer contains an α-olefinselected from ethylene and butene.

The polypropylene elastomer may exhibit a Shore A hardness (i.e.,durometer) as measured according to ASTM D 2240-05 of at least about 40,more preferably at least about 50, still more preferably at least about65. The Shore A hardness may also be less than about 97, preferably lessthan about 95, more preferably less than about 92, still more preferablyless than about 85 (e.g., less than about 80). For example, thepolypropylene elastomer may have a Shore A hardness from about 40 toabout 97, more preferably from about 50 to about 95, and still morepreferably from about 65 to about 95 Shore A.

Suitable polypropylene elastomer may have a melt flow rate as measuredaccording to ASTM D1238 at 230° C./2.16 kg of at least 1, preferably atleast about 4, more preferably at least about 7, and most preferably atleast about 10 g/10 min. Without limitation, the propylene elastomerssuitable for the polymeric composition may have a melt flow rate of lessthan about 1500, preferably less than about 150, more preferably lessthan about 100, and most preferably less than about 60 g/10 min.

It is preferred that the polypropylene elastomer exhibit at least somecrystallinity The crystallinity may be at least about 2, preferably atleast about 5, and still more preferably at least about 7 percent byweight of the polypropylene elastomer material. Without limitation,suitable polypropylene elastomers may have a crystaiiinity less thanabout 50 wt. % For example, the crystallinity of the propylene elastomermay be less about 40, preferably less than about 35, more preferablyless than about 28, and still more preferably less than about 20 percentby weight of the polypropylene elastomer material, in general, suitablepropylene elastomer may have a crystallinity from about 2 wt. % to about50 wt. %. For example, the crystallinity may range from about 2 to about40, more preferably from about 5 to about 35, and still more preferablyabout 7 to about 20 percent by weight of the polypropylene elastomermaterial.

If the propylene elastomer is a copolymer of propylene and ethylene(i.e., the comonomer is ethylene) then it will be appreciated from theabove that the resulting preferred overall compositions (i.e., thepolymeric composition) which include a propylene elastomer willtherefore have an ethylene content (i.e., a total ethylene content). Forexample, in one aspect the overall ethylene content in the finalresulting composition may be greater than about 2 percent by weight ofthe overall resulting composition, preferably greater than about 3percent by weight of the overall resulting composition, and morepreferably greater than about 4 percent by weight of the overallresulting composition. In this aspect of the invention, it is generallyexpected however the total concentration of ethylene in the overallresulting composition will be less than about 35 percent by weight ofthe overall composition, preferably less than about 25 percent by weightof the overall composition, more preferably less than about 20percent byweight of the overall composition, and still more preferably less thanabout 10 percent by weight of the overall resulting composition.

If the propylene elastomer is a copolymer of propylene and a C₄-C₁₂α-olefin (e.g., butane, hexane, or octane), then it will be appreciatedfrom the above that the resulting preferred overall compositions (i.e.,the polymeric composition) which include a propylene elastomer willtherefore have a total C₄-C₁₂ α-olefin, for example, in one aspect theoverall C₄-C₁₂ α-olein content in the final resulting composition may begreater than about 2 percent by weight of the overall resultingcomposition, preferably greater than about 3 percent by weight of theoverall resulting composition, and more preferably greater than about 4percent by weight of the overall resulting composition. In this aspectof the invention, it is generally expected however that the totalconcentration of C₄-C₁₂ α-olefin in the overall resulting compositionwill be less than about 35 percent by weight of the overall composition,preferably less than about 25 percent by weight of the overallcomposition, more preferably less than about 20 percent by weight of theoverall composition, and still more preferably less than about 10percent by weight of the overall resulting composition.

Other examples of suitable elastomers which may be used in the secondpolymeric component include elasfomeric polymers containing greater thanabout 50 wt. % (e.g., greater than 60 wt. %) propylene monomer andgreater than about 5 wt. % ethylene monomer and may be characterized bya peak melting temperature from about 35° C. to about 130° C. (e.g. fromabout 40° C. to about 110° C.) as measured by differential scanningcalorirnstry. Such elastomers are commercially available from THE DOWCHEMICAL COMPANY under the designation of VERSIFY® (e.g., including2400, 3000, 3200, 3300, 3401, and 4301) and from EXXONMOBIL CHEMICALCOMPANY under the designation of VISTAMAXX®.

Additional specific examples of propylene elastomers that may beemployed in accordance with the present teachings include thosedisclosed in WO 03/040201 A1 filed on May 6, 2002, published USApplication No. 2003-0204017 filed on May 5, 2002, and U.S. Pat. No.6,525,137 issued on Feb. 25, 2003, all of which are incorporated intheir entirety by reference.

For example, the propylene elastomer may include a Low ElasticityEthylene-Propylene Copolymer (LEEP Copolymer) as described in U.S. Pat.No. 6,525,157. Suitable LEEP Copolymer may contain from a lower limit of5% or 6% or 8% or 10% by weight to an upper limit of 20% or 25% byweight ethylene-derived units, and from a lower limit of 75% or 80% byweighl to an upper limit of 95% or 94% or 92% or 90% by weightpropylene-derived units, the percentages by weight based on the totalweight of propylene-and ethylene-derived units. The copolymer issubstantially free of diene-derived units.

In various embodiments, features of the LEEP Copolymers include some orall of the following characteristics, where ranges from any recitedupper limit to any recited lower limit ere contemplated:

(i) a melting point ranging from an nppar limit of less than 110° C., orless than 90° C., or less than 80° C., or less than 70° C., to a lowerlimit ol greater than 25° C., or greater than 35° C., or greater than40° C., or greater than 45° C.;

(ii) a relationship of elasticity to 500% tensile modulus such thatElasticity≦0.935M+12, or Elasticity≦0.935M+6, or Elasticity≦0.935M,where elasticity is in percent and M is the 500% tensile modulus in megaPascal (MPa);

(iii) a relationship of flexural modulus to 500% tensile modulus suchthat Flexural Modulus≦4.2e^(0.27M)+50, or Flexural Modulus≦42e^(0.27M)+, or Flexural Modulus≦4.2e^(0.27M)+10, or FlexuralModulus≦4.2e^(0.27M)+2, where flexural modulus is in MPa and M is the500% tensile modulus in MPa;

(iv) a heat of fusion ranging from a lower limit of greater than 1.0Joule per gram (J/g), or greater than 1.5 J/g, or greater than 4.0 J/g,or greater than 6.0 J/g, or greater than 7.0 J/g, to an upper limit ofless than 125 J/g, or less than 100 J/g, or less than 75 J/g, or lessthan 60 J/g, or less than 50 J/g, or less than 40 J/g, or less than 30J/g;

(v) a triad tacticity as determined by carbon-13 nuclear magneticresonance (¹³C NMR) of greater than 75%, or greater than 80%, or greaterthan 85%, or greater than 90%;

(vi) a tacticity index m/r ranging from a lower limit of 4 or 6 to anupper limit of 8 or 10 or 12;

(vii) a proportion of inversely inserted propylene units based on 2.1insertion of propylene monomer in all propylene insertions, as measuredby ¹³C NMR of greater than 0.5% or greater than 0.6%;

(viii) a proportion of inversely inserted propylene units based on 1.3insertion of propylene monomer in all propylene insertions, as measuredby ¹³C NMR, of greater than 0.05%, or greater than 0.06%, or greaterthan 0.07%, or greater man 0.08%, or greater than 0.085%;

(ix) an intermolecular tacticity such that at least X % by weight of thecopolymer is soluble in two adjacent temperature fractions of a thermalfractionation carried out in hexane in 8° C. increments, where X is 75,or 80, or 85, or 90, or 95, or 97, or 99;

(x) a reactivity ratio product r₁r₂ of less than 1.5, or less than 1.3,or less than 1.0, or less than 0.8;

(xi) a molecular weight distribution Mw/Mn ranging from a lower limit of1.5 or 1.6 to an upper limit of 40 or 20 or 10 or 5 or 3;

(xii) a molecular weight of from: 15,000-5,000,000;

(xiii) a sold stale proton nuclear magnetic resonance (¹H NMR)relaxation time of less than 18 milliseconds (ms), or less than 18 ms,or less than 14 ms, or less than 12 ms, or less than 10 ms;

(xiv) an elasticity as defined herein of less than 30%, or less than20%, or less than 10%, or less than 8%, or less than 5%; and

(xv) a 500% tensile modulus of greater than 0.5 MPa, or greater than 0.8MPa, or greater than 1.0 MPa, or greater than 2.0 MPa.

The LEEP Copolymer may be made in the presence of a bridged metallocenecatalyst, in a single steady-state reactor.

The test methods for the LEEP Copolymer are described in U.S. Pat. No.6,525,157.

Another example of a propylene elastomer which may be used is aregion-error containing propylene-ethylene copolymer (i.e., a R-EPEcopolymer) as described in U.S. Patent Application Publication No.2003/0204017 (published Oct. 30, 2003).

As disclosed in U.S. Patent Application Publication No. 2003/0204017(published Oct. 30, 2003) paragraph [0007], the R-EPE copolymers may becharacterized as comprising at least about 60 weight percent (wt. %) ofunits derived from propylene, about 0.1-35 wt % of units derived fromethylene, and 0 to about 35 wt % of units derived from one or moreunsaturated comonomers, with the proviso that the combined weightpercent of units derived from ethylene and the unsaturated comonomerdoes not exceed about 40. These copolymers are also characterized ashaving at least one of the following properties: (i) ¹³C NMR peakscorresponding to a regio-error at about 14.6 and about 15.7 ppm, thepeaks of about equal intensity, (ii) a B-value greater than about 1.4when the comonomer content, i.e., the units derived from ethylene and/orthe unsaturated comonomer(s), of the copolymer is at least about 3 wt %,(ill) a skewness index, S_(ix) greater than about −1.20, (iv) a DSCcurve with a T_(me) that remains essentially the same and a T_(max) thatdecreases as the amount of comonomer, i.e., the units derived fromethylene and/or the unsaturated comonomer(s), in the copolymer isincreased, and (v) an X-ray diffraction pattern that reports moregamma-form crystals than a comparable copolymer prepared with aZiegler-Natta (Z-N) catalyst. Typically the copolymers of thisembodiment are characterized by at least two, preferably at least three,more preferably at least four, and even more preferably all five, ofthese properties. The test methods for the R-EPE are disclosed in U.S.Patent Application Publication No. 2003/0204017.

S/LEPs

The second polymeric component herein may employ one or more otheralpha-olefin elastomers, such as one or more linear ethylene copolymersor interpolymers (also known as “LEPs”), one or more substantiallylinear ethylene copolymers or interpolymers (also known as “SLEPs”), orboth. As used herein, SLEPs typically include LEPs. Substantially linearethylene copolymers and linear ethylene copolymers and their method ofpreparation are fully described in U.S. Pat. Nos. 5,272,236; and5,278,272, which are fully incorporated herein by reference for allpurposes.

As used herein, “a linear or substantially linear ethylene polymer”means a copolymer of ethylene and one or more alpha-olefin comonomershaving a linear backbone, a specific and limited amount of long-chainbranching or no long-chain branching, a narrow molecular weightdistribution, a narrow composition distribution (e.g., for alpha-olefincopolymers) or a combination thereof. More explanation of such polymersis discussed in U.S. Pat. No. 6,403,692, which is incorporated herein byreference for all purposes.

Illustrative alpha-olefins include propylene, 1-butene, 1-hexene,4-methyl-1-pentene, 1-heptene, 1-octane, 1-decene, 1-dodecene,1-hexadodecene, 4-methyl-1-pentene, 2-methyl-1-butene,3-methyl-1-butene, 3,3-dimethyl-1-butene, diethyl-1-butene,trimethyl-1-butene, 3-methyl-1-pentene, ethyl-1-pentene,propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene,diethyl-1-hexene, bimethyl-1-pentene, 3-methyl-1-hexene,dimethyl-1-hexene, 3,3,5-trimethyl-1-hexene, methylethyl-1-heptene,trimethyl-1-heptene, dimethyloctene, ethyl-1-octane, methyl-1-nonene,ethylene-octene, vinylcyclopentene, vinylcydoliexene andvinylnorbornene, where alkyl branching position is not specified if isgenerally on position 3 or higher of the alkene and styrene. Thealpha-olefin is desirably a C₃-C₂₀ or C₃-C₁₀ alpha-olefin. Preferredcopolymers include ethylene-propylene (EP), ethylene-butene (EB),ethylene-hexene-1 (EH), and ethylene-oxide (EO) polymers, illustrativeterpolymers include an ethylene/propylene/octene ferpolymer as well asterpolymers of ethylene, a C₃-C₂₀ alpha-olefin and a diene such asdicyclopentadiene, 1,4-haxadiene, piperylene or5-ethylidene-2-norbornene.

The SLEP may include one or more higher alpha-olefin containing at least8 carbon atoms. For example, suitable higher alpha-olefins may includeone or more alpha-olefins containing from 8 to about 20 carbon atoms,more preferably one or more alpha-olefins containing from about 8 toabout 12 carbon atoms. The higher alpha-olefin may include or consistessentially of 1-octene. Without limitation, exemplary SLEPs may containgreater than about 50 wt. %, and preferably greater than about 55 wt. %ethylene monomer based on the total weight of the SLEP. Exemplary SLEPsmay contain less than about 85 wt. %, preferably less than about 80% andmora preferably, lass than about 70 wt. % ethylene monomer based on thetotal weight of the SLEP. The concentration of the higher alphaolefin inthe SLEP may be greater than about 12 wt. %, more preferably greaterthan 20 wt. %, and most preferably greater than about 30 wt. % based onthe total weight of the SLEP. For example, the SLEP may be a copolymerwhich contains ethylene monomer at a concentration greater than about 50wt. % and 1-octane monomer at a concentration greater than about 12 wt.% (e.g. greater than about 20 wt. %) based on the total weight of theSLEP. Suitable SLEPs are commercially available from THE DOW CHEMICALCOMPANY under the designation of Engage®.

One preferred S/LEP for use in the second polymeric component includesone or more elastomers including an ethylene content having a density ofbetween about 0.8 to about 0.9 g/cm³ (e.g., from about 0.855 to about0.895 g/cm³) according to ASTM D 792-00. Suitable S/LEPs may have adensity of at least 0.855, preferably at least 0.860, more preferably atleast 0.865, most preferably at least 0.867 g/cm³. The density of theS/LEPs may be less than about 0.908, preferably less than about 0.895,more preferably less than about 0.890, and most preferably less thanabout 0.880 g/cm³. Densities are determined as measured by ASTM D792-00. In one aspect of the invention, suitable S/LEPs will desirablyexhibit a melt flow rate that makes it compatible for melt blending withthe first polymeric component. For example, the ethylene elastomer mayexhibit a melt flow rate according to ASTM D-1238-04c (at 230° C., 2.16kg) of at least about 0.6, more preferably at least about 3, and stillmore preferably at least about 5 g/10 min. The melt flow rate also maybe below about 60, more preferably below about 40, and still morepreferably below about 30 g/10 min. For example, the melt flow rate mayrange from about 0.5 to about 60, more preferably from about 3 to about40, and still more preferably about 5 to about 30 g/10 min.

The composition of the present invention further contemplates a secondpolymeric component that includes an ethylene content and preferablyincludes at least one soft thermoplastic which contains ethylene.Suitable soft thermoplastics which may be used in the second polymericcomponent may have a phase transition (e.g., a peak melting temperature,or a glass transition temperature) at a temperature greater than about40° C. (e.g. at least a portion of the elastomer is crystalline). Thesoft thermoplastic may have a crystallinity from about 2% to about 14%,more preferably from about 3% to about 11% and most preferably fromabout 4% to about 9%, although soft thermoplastics having higher orlower crystallinity may be used.

The second polymeric component (e.g., the S/LEP, or even the propylenecontaining elastomer) may contain a polymer having a peak meltingtemperature (as measured for example by differential scanningealorimetry at a rate of about 10° C./min on a 3 mg sample of thepolymer which is first cooled from 230° C. to about 0° C. at a rate of−10° C./min) less than about 105° C., preferably less than about 100°C., more preferably less than about 90° C., and most preferably lessthan about 82° C. (e.g., the peak melting temperature may be less thanabout 65° C.).

Suitable S/LEPs for the second polymeric component may exhibit a Shore Ahardness according to ASTM D2240-05 of at least about 45, preferably atleast about 55, more preferably at least about 60, and still morepreferably at least about 65. The Shore A hardness may also be less thanabout 95, preferably less than about 90, more preferably less than about85, and still more preferably less than about 80. For example, theelastomer may range from about 65 to about 95, more preferably fromabout 65 to about 85, and still more preferably from about 65 to about80.

One preferred S/LEP for use in the second polymeric component includesone or more elastomers including an ethylene content having a density ofbetween about 0.8 to about 0.9 g/cm³ (e.g., from about 0.855 to about0.895 g/cm³) according to ASTM D 792-00. Suitable S/LEPs may have adensity of at least 0.855, preferably at least 0.860, more preferably atleast 0.865, most preferably at least 0.867 g/cm³. The density of theethylene elastomer may be less than about 0.908, preferably less thanabout 0.895, more preferably less than about 0.890, and most preferablyless than about 0.880 g/cm³. Densities are determined as measured byASTM D792-00. In one aspect of the invention, suitable S/LEPs willdesirably exhibit a melt flow rate that makes it compatible for meltblending with the first polymeric component. For example, the ethyleneelastomer may exhibit a melt flow rate according to ASTM D-1238-04c (at230° C., 2.16 kg) of at least about 0.5, more preferably at least about3, and still more preferably at least about 5 g/10 min. The melt flowrate also may be below about 60, more preferably below about 40, andstill more preferably below about 30 g/10 min. For example, the meltflow rate may range from about 0.5 to about 60, more preferably fromabout 3 to about 40, and still more preferably about 5 to about 30 g/10min.

Reinforcement Material

The composition of the present invention further includes areinforcement material and particularly a reinforcement material, suchas one or more glass fibrous materials (e.g., short glass fibers, longglass fibers, or both), or other fibers (e.g., steel, carbon, the like,or otherwise), platelets (e.g., talc, wollastonite, the like, orotherwise), or combinations thereof. Preferably, the fibers will besubstantially, uniformly distributed throughout the final composition.However, it may be possible to selectively locate fibers in one or morepredetermined locations within the compositions.

The overall polymeric composition typically includes at least about 10,and more typically at least about 20 parts by weight of the fibrousreinforcement material. The overall polymeric composition also typicallyincludes less than about 70, more typically less than about 50, andstill more typically less than about 40 parts by weight of the fibrousreinforcement material.

It will be appreciated that in resulting final composition (e.g., in theresulting compositions or articles following a shaping step such asinjection molding), fiber lengths may be reduced relative to the initialfiber length. Examples of average fiber lengths in the final compositionrange from above about 0.5 mm, and more specifically above about 1 mm,e.g., from about 0.5 to about 5 mm, or more specifically greater than 1mm to about 3 mm in length (e.g. about 1 mm to about 2 mm). Preferably,at least about 50 percent by weight of the fibers will be longer than 1mm, and more preferably at least about 65 (or even about 75) percent byweight of the fibers will be longer than about 1 mm (or even longer thanabout 4 mm). Fiber diameters typically will range from about 3 to about100 microns, and more specifically about 5 to about 25 microns (e.g.,about 17 microns). The glass may be one or more of E-glass, S-glass,T-glass, AR-glass, C-glass, R-glass or otherwise.

It is also contemplated that the polymeric composition optionally caninclude one or more additives such as a surfactant, a flexibizer, acoupling agent, a flame retardant, an ignition resistant additive, astabilizer, a colorant, an antioxidant, a mold release agent, ananti-static agent, a slip-aid (i.e., slip resistance aid), a flowenhancer, a nucleating agent, a clarifying agent, or any combinationthereof. For example, one or more pigments or colorants may be added tothe polymeric composition such that the parts or components are“molded-in-color.” By way of example, colorants may be added to thefibrous reinforcement material. One preferred additive is a colorant,which when included is present, in a relatively small weight percentageof the overall resulting composition (e.g., less than about 5 weightpercent or even less than about one weight percent). For example, thecolorant may be for achieving a black appearance, a gray flannelappearance, or otherwise. Preferred examples of additives are ignitionresistance additives, such as, but not limited to halogenatedhydrocarbons, halogenated carbonate oligomers, halogenated diglycidylethers, organophosphorous compounds, fluorinated olefins, antimony oxideand metal salts of aromatic sulfur, or a mixture thereof may be used.Further, compounds which stabilize thermoplastic compositions againstdegradation caused by, but not limited to heat, light, and oxygen, or amixture thereof may be used. One preferred additive is antioxidant,which, when included, is typically included in a relatively small weightpercentage of the overall polymeric composition (e.g., less than about 1or 2 percent). An example of one preferred commercially availableantioxidant is IRGANOX B225 antioxidant commercially available from CibaSpecialty Chemicals Corporation. Irganox B225 antioxidant is a blend of1 part Irganox 1010 antioxidant(Tetrakis(methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane) and1 part Irgafos 168 tris(2,4-t-butylphenyl) phosphite. Another preferredadditive is a demolding agent (e.g. a wax, mold relief, sip-aid, thelike, or otherwise.). One preferred demolding agent is a nitrogen orammonia group containing compound such as an amine or an amide. Onepreferred amide containing compound is ethylene bisstearamide (EBS).Another preferred category of mould release agents is “stearates” suchas Glycerol MonoStearate commercially available from Danisco or CibaSpecialty Chemicals under the tradename Atmer. One preferred nitrogencontaining compound, which is a wax, is an erucamide sold under thetradename KENAMIDE ULTRA E, commercially available from ChemturaCorporation, Middlebury, Conn.

One preferred additive is a coupling agent, e.g., a graftedpolypropylene coupling agent such as maleic anhydride, graftedpolypropylene coupling agent (e.g., Polybond 3200 from Chemtura orOREVAC CA-100 from Arkema). Optionally, the polymeric composition of thepresent invention may include a coupling agent or be free of a couplingagent. When included, the coupling agent will be present in theresulting overall composition in an amount less than about 5 percent byweight, and more preferably less than about 2 percent by weight. Forexample, it may be present in an amount of at least 0.01 percent byweight or even at least about 0.1 percent by weight of the overallcomposition.

As discussed herein, the polymeric composition of the present inventionincludes a first polymeric component, a second polymeric component, anda fibrous reinforcement material. It will be appreciated that a ratio ofthe first polymeric component with respect to the second polymericcomponent does not exceed 1:4.2, and more specifically does not exceed1:2.7. Preferably, the ratio ranges from about 5:1 to about 1:4.2, morepreferably about 5:1 to about 1:2.7 of the first polymeric component tothe second polymeric component.

The resulting polymeric compositions herein can be prepared according toany suitable technique for achieving the desired properties in a blendedcompound. Combinations of two or more ingredients may be compounded(e.g., first polymeric component and reinforcement material) prior tofeeding the materials to processing epulpoient (e.g., beforeintroduction into an injection molding apparatus). Alternatively, or inaddition, two or more of the ingredients may be compounded with eachother while within the processing equipment. For example, the polymericcomponents of the resulting composition are not melt-blended with eachother until they are in the processing equipment (e.g., within a screwand barrel assembly, a mixing nozzle, injection machine, the like orotherwise). Preparation of the compositions of this invention can beaccomplished using any suitable mixing means, including dry blending twoor more of the individual components, melt blending, or both eitherdirectly in an apparatus used to make the finished article (e.g., theautomotive part), or in a separate apparatus (e.g., pramixing in aBanbury mixer). Dry blends of the compositions can also be directlyinjection molded without pre-melt blending step. In one preferredembodiment, the formation of the polymeric composition includes mixingat least two components (e.g., the second polymeric component and thereinforcement concentrate) or mixing at least three components (e.g.,first polymeric component, second polymeric component, and thereinforcement material) at the molding machine, (e.g. blending at thepress). Optionally or in addition to, two or more ingredients maypre-compounded in a compounding unit prior to mixing at the moldingmachine.

As discussed above, the ingredients in the polymeric composition mayalso be compounded or melt blended in a mixer such as Banbury mixer, orin an extruder such as a kneader, a compounding single screw extruder, atwin screw extruder, a heated two-roll mill, and the like. In one aspectof the invention, after compounding the ingredients, the blendedpolymeric material may be palletized to form granules or pellets whichare capable of being fed into a molding machine. A quantity (e.g.,greater than 5 kg, preferably greater than 20 kg, or even greater than250 kg) of the pellets or granules may be placed in a container, andstored or transported prior to molding an article.

When softened or melted by the application of heat, the polymericcompositions of this invention can be fabricated into articles usingconventional techniques such as compression molding, injection molding,gas assisted injection molding, calendering, vacuum forming,thermoforming, extrusion, blow molding, alone or in combination. Thepolymeric compositions can also be formed, spun, or drawn into films,fibers, multi-layer laminates or extruded sheets, or can be compoundedwith one or more organic or inorganic substances, on any machinesuitable for such purpose. In a particularly preferred embodiment, thepolymeric compositions of the present invention are preferably injectionmolded to form a shaped resulting article, with or without anaccompanying insert (e.g., as part of an insert molding process), or aspart of an over-molded article.

In one preferred embodiment, it is contemplated that the first polymericcomponent and the second polymeric component (e.g., the softthermoplastic), are not pre-compounded with each other in molten stateprior to feeding them to an apparatus for preparing a shaped article.Rather they are admixed with each other, and first subjected tomelt-blending, only upon being introduced to the apparatus (e.g., duringmixing in a screw and barrel assembly of an injection molding machine).

It is possible the reinforcement material may be added in a looseindividual state, or even as bundles of materials (e.g., fibers).Preferably, the reinforcement material is incorporated into the mixtureas part of a cohesive concentrate form that includes the reinforcementmaterial dispersed in a matrix of polymeric material that is compatiblewith or the same as the other polymeric components (e.g., firstpolymeric component) of the resulting overall composition. By way ofexample, if is contemplated that a fibrous (e.g., glass fibers)reinforcement concentrate may be utilized, wherein the fibrous phase isdistributed in a polymeric matrix phase, such as a matrix phase thatincludes one or mom of the polymeric material discussed herein, such asa polypropylene homopolyrner. The fibrous phase is present in an amountof at least about 20 percent by weight, and more preferably greater than50 percent by weight (e.g., about 50 to about 90 percent by weight, suchas about 60 percent by weight) of the concentrate. An example of onesuch concentrate of fibrous reinforcement material is discussed in U.S.Patent Application Ser. No. 60/890,002, filed Aug. 16, 2007, which ishereby incorporated by reference for all purposes.

It is contemplated in one exemplary embodiment, that the polymericcomposition may include the first polymeric component, the secondpolymeric component having an ethylene content, and the reinforcementconcentrate having the reinforcement material and the polymeric msifmthat includes additional polymeric material. In another exemplaryembodiment, the polymeric composition may include the second polymericcomponent having an ethylene content, and the reinforcement concentratehaving a polymeric matrix that includes the first polymeric component.

One approach is to employ fibers that are pre-treated or otherwisemodified to improve one or more of their characteristics. For example,one approach is to coat the fibers with a chemical agent (e.g., acoupling agent, a surface property modifier, a stabilizer, or othersuitable agent). By way of one specific example, fibers may be treatedwith a sizing agent for physically, chemically, or both improving thetenacity of the subsequent interfacial bond with a polymeric matrix, forprotecting the surface of the fibers from damage or both. The sizingwill typically include a suitable film forming agent, a coupling agent(e.g., a silane such as an alkoxysilane), and optionally a lubricant orother agent. It may be possible to include for at least part of thesizing a coupling agent as described previously (e.g., including amaleic anhydride grafted polypropylene coupling agent).

Fibers may be provided as individual fibers, chopped and/or continuousfibers, that are randomly oriented relative to each other, axiallyaligned relative to each other, woven, or any combination thereof, andwhich may thereafter be dispersed into the polymeric matrix, (e.g., athermoplastic polymeric matrix, such as one including a polypropylenehomopolymer or copolymer), it is also contemplated that the fibers willbe provided in a bundle, by which the fibers are generally axiallyaligned.

The fibrous reinforcement concentrate material herein may be anysuitable size or shape. In general, it may be elongated (e.g., as arod), granular, substantially symmetrical in shape about at least oneaxis, substantially asymmetrical in shape about at least one axis,substantially solid, porous, or any combination thereof. Individualparticles of the fibrous reinforcement concentrate material may havetheir largest dimension, (e.g., length, diameter, height, width,thickness, or otherwise), about 5 mm or larger, more specifically about8 mm or larger, and still more specifically about 10 mm or longer.Smaller sizes are also possible as well, such as less than about 1 mm,and more specifically less than about 0.5 mm.

One approach to the manufacture of the fibrous reinforcement concentrateis to impregnate a fiber bundle with the polymer such as by artdisclosed pultrusion techniques. See e.g., U.S. Pat. No. 5,834,056“Process and Apparatus for Fiber Bundle Impregnation,” which is herebyincorporated by reference for all purposes.

In general, the invention herein contemplates the manufacture of ashaped article, pursuant to which the first polymeric component, thesecond polymeric component, and the reinforcement concentrate are fedfrom individual sources (e.g., hoppers) info a screw and barrel assemblyof a processing apparatus. As the material travel along the assembly,they are subject to shear and heat for causing them to melt blend witheach other. Optionally, a mixing nozzle is also employed in theapparatus for assisting to melt blend. The resulting melt blendedingredients are introduced into a tool that shapes the material (e.g., adie, a mold, or other structure for imparting a shape to the introducedmaterial).

Advantageously, it has been surprisingly found that desired properties(e.g., low gloss and improved mar resistance, scratch resistance, lowtemperature ductility, and dimensional stability, or otherwise) can beachieved by the disclosed proportions of the fibrous reinforcementconcentrate, the first polymeric component, the second polymericcomponent. By way of example, articles formed compositions from thepresent invention will achieve an article having a soft-touch feeltactile surface with superior grain reproduction (e.g., low gloss) andimproved mar resistance compared to articles formed compositions knownin the art. More specifically, it has been found that the article formedusing a fool with an N111 texture (e.g., an Opel N111 texture) fromcompositions of the present invention may achieve improvedcharacteristics of gloss (e.g., gloss measured on a N111 texture withmicro matt) according to ASTM D-542 that ranges from about 0.6 to about1.7 GU, more specifically about 0.9 to about 1.4 GU. Furthermore, it hasbeen found that the article formed using the compositions of the presentinvention may achieve improved characteristics for mar resistance (e.g.,mar at 6N according to GMW 14688 of less than about 2 GU, and possiblybetween about 0.05 and about 1 GU; scratch resistance (e.g., scratch at10N measured on an article formed having an N111 texture with micro mattaccording to PV3952 of less than about 1 dL, more typically less thanabout 0.5 dL; scratch at 10 N (article formed having an Audi K42texture) according to PV3952 of less than about 0.4 dL, dimensionalstability (e.g., shrinkage of less than about 5% and possibly between0.1% to about 1%; coefficient of linear expansion (CLTE) in flowaccording to ASTM D-696 ranging from about 25 to about 50 mm/mm° C. andmore specifically from about 30 to about 45 mm/mm° C.; and coefficientof linear expansion (CLTE) cross flow according to ASTM D-696 rangingfrom about 40 to about 70 mm/mm° C. and more specifically from about 45to about 65 mm/mm° C.), or combinations thereof. Preferably,advantageous results are achieved wherein the polymeric composition isfree of grafted co-polymers, free of mineral filler (e.g., talc), freeof glass particles other than glass fibers, free of peroxides, or anycombination thereof.

The polymeric composition of the present invention finds manyadvantageous applications. The present invention accordinglycontemplates articles made with the present composition and methods thatinclude one or more steps of shaping the compositions to form articles.The articles typically will be shaped. They may have a substantiallyconstant profile along their lengths (e.g., from extrusion). They mayhave shapes that vary throughout the article (e.g., to include one ormore surfaces that are flat, contoured, or a combination thereof. Thearticles herein may be composite articles. They may be articles that areinsert molded, over molded, or both. For example, the present inventioncan be employed as part of a variety of articles of manufacture,however, it has already been found particularly suitable for use informing articles such as a tray, a table, a plate; lawn and gardenfurniture, a shoe, a boot, or the like. The polymeric composition mayalso be used to form automotive parts such as dash board, consoles, armrests, switch covers, brake levers, shifters, knobs, handles, controlbuttons, trim panels, seat back covers, instrument housings, cupholders, a panel, sun visor, rear view mirror housing, fascia (e.g.,bumper fascia), automotive trim, automotive cowling, console (e.g.,center overhead, floor assemblies, or both), instrument, panel, glovebox assemblies including doors, knee bolster assemblies or instrumentpanel retainer assemblies or structural components.

Materials resulting from the teachings herein will have any combinationof at least one, two (and more specifically at least 3 or all) of thefollowing properties; namely, a flexural modulus in flow according toISO 178 that ranges from about 200 to about 4000 MPa and morespecifically about 350 to about 3500 MPa; flexural modulus in cross flowaccording to ISO 178 that ranges from about 50 to about 2500 MPa andmore specifically about 150 to about 1950 MPa; average flexural modulusaccording to ISO 178 that ranges from about 50 to about 3000MPa and morespecifically about 150 to about 2000 MPa; Charpy Impact notched RTaccording to ISO 179-1eU that ranges from about 5 to about 50 kJ/m² andmore specifically about 11 to about 45 kJ/m²; Charpy impact notched −20°C. according to ISO 179-1eU that ranges from about 1 to about 35 kJ/m²and more specifically about 4 to about 28 kJ/m²; Coefficient of Friction(static) according to ASTM D-1894 that ranges from about 0.2 to about0.7 and more specifically about 0.1 to about 0.6; and Coefficient ofFriction (dynamic) according to ASTM D-1894 that ranges from about 0.5to about 0.75 and more specifically about 0.2 to about 0.5. It should beappreciated that the average flexural modulus is the average of thein-low and cross-flow modulus. By way of example, the average flexuralmodulus may be obtained by the cutting off test bars from a moldedplague having a film gate on one side. The test bars that are cut alongthe direction of the film gate are used for determining the in-flowmodulus and the test bars that are cut perpendicular to the flow areused to determine the cross-flow modulus.

EXAMPLES Examples 1-6

Examples (EX.) 1 through 6 are prepared by injection molding thecompositions of TABLE 1. The first polymeric component (a polypropylenehomopolymer), the second polymeric component (a propylene-ethyleneelastomer), and the reinforcement concentrate (containing long glassfiber and additional first polymeric component polypropylene) are dryblended and then introduced into a DEMAG 100 injection molding machine,in which they are melt-blended (i.e., the solid, dry-blended pellets,after being introduced into the screw of the injection molding machinemelt and become blended) prior to injection into a mold cavity forforming the test samples. The data in TABLE 1 illustrates the expectedresults.

Examples 7-15

EXAMPLES 7 through 15 are prepared using the same procedure as EXAMPLES1-6, using the formulation given in TABLE 2. In addition to the firstcomponent, the second component and the reinforcement material, EXAMPLES7 through 15 also include a color concentrate which is dry blended withthe other ingredients and then introduced into the DEMAG injectionmolding machine, data in TABLE 2 illustrates the expected results.

Examples (EX.) 16-23 and Comparative Example (C.E.) 24

Molded parts are prepared by injection molding the compositions of TABLE3 using the same method as used in EXAMPLES 7 through 15, in EX. 16-22,the second polymeric component is a S/LEP, and specifically anethylene-ocfeoe copolymer. EX. 23 uses a propylene-ethylene elastomer asthe second polymer component. C.E. 24 is a comparative example whichincludes talc instead of the long glass fiber containing reinforcementconcentrate.

TABLE 1 Method Units EX. 1 EX. 2 EX. 3 EX. 4 EX. 5 EX. 6 IngredientReinforcement 42 42 42 42 42 42 Cocentrate-A Elastomer A 44.9 25 15Elastomer B 58 42 Elastomer C 58 PP-A 13.1 PP-B 33 43 16 Total 100 100100 100 100 100 Property Ethylene Content in 15 15 15 9 9 5 Elastomer(%) Average Flexural ISO 178 MPa 1228 2252 2673 1609 1794 1861 ModulusCharpy RT ISO 179- kJ/m2 39 23 24 29 20 17 1eU Charp −20 C. ISO 179-kJ/m2 25 12 13 14 12 10 1eU VICAT Softenting ISO 6603-3 ° C. 80 116 8797 Point-50/5 VICAT Softening ISO 6603-3 ° C. 120 162 164 126 160 160Point-120/10 Gloss (N111 texture ASTM D- GU 1.0 1.1 1.1 0.9 1.0 1.0 withmicro matt) 542 Mar 6N (N111 texture GMW 14688 dGU 0.2 0.3 0.3 0.2 0.20.2 with micro matt)

S/LEP-A is a copolymer containing about 59 wt. % ethylene monomer unitsand about 41 wt. % octene monomer units. This ethylene elastomer has aspecific gravity of about 0.868 as measured according to ASTM D792, ahardness of about 70 Shore A as measured according to ASTM D2240, a peakmelting temperature of about 55° C. as measured by differential scanningcalorimetry, a flexural modulus of about 14.4 MPa as measured accordingto ASTM D790 (using compression molded samples and tested at 2% secant),a melt flow rate of about 0.5 g/10 min as measured according to ASTMD1238 at 190° C./2.16 kg, a tensile strength at 100% strain of about 2.6MPa as measured according to ASTM D638 at a strain rate of 510 mm/min, atensile strength at break of about 9.5 MPa as measured according to ASTMD638 at a strain rate of 510 mm/min, a tensile elongation at break ofabout 810% as measured according to ASTM D638 at a strain rate of 510mm/min, and a Vicat softening point of about 46° C. as measuredaccording to ASTM D1525.

TABLE 2 Ex. Ex. Ex. Ex. Ex. Ex. Ex. 7 Ex. 8 Ex. 9 10 11 12 13 14 15Reinforcement Concentrate-A 42 42 42 42 42 42 42 42 42 Elastomer A 43.144.9 44.9 46.7 Elastomer B 46.7 54 Elastomer D 43.1 44.9 44.9 PP-A 10.99.1 7.3 10.9 9.1 7.3 PP-B 9.1 9.1 CC-A 4 4 4 4 4 4 4 4 4 Total 100 100100 100 100 100 100 100 100 Property, Method (Units) Ethylene Content inElastomer 15 15 15 15 12 12 12 9 9 (wt. %) Flexural Modulas in Flow 9551225 1225 888 1986 1684 1561 2044 1836 Direction, ISO 178 (MPa) StaticCoefficient of Friction, 0.43 0.38 0.43 0.42 0.37 0.38 0.38 0.32 0.32ASTM D-1894 Dynamic Coefficient of Fricton, 0.35 0.33 0.38 0.37 0.310.34 0.33 0.25 0.28 ASTM D-1894 Hardness, ASTM D-2250 45 44 44 42 53 5252 59 56 (Shore D) Gloss (N111 texture with micro 1.4 1.4 1.3 1.3 1.31.4 1.3 1.2 1.2 matt), ASTM D-542 (GU) Mar 6N (N111 texture with 0.4 0.40.6 0.5 micro matt), GMW 14688 (GU) scratch 10N (Audi K42 0.2 0.16 0.150.27 0.11 texture), PV3952 (dL) Vicat Softening Point - 120/10, 88 84 80104 105 112 135 119 ISO 6603-3 (° C.) Charpy at RT, ISO 179-1eU 28 15 11(KJ/m²) Charpy at −20° C., ISO 179-1eU 14 7 6 (KJ/m²)

S/LEP-B is a copolymer containing about 59 wt. % ethylene monomer unitsand about 41 wt. % octane monomer units. This ethylene elastomer has aspecific gravity of about 0.870 as measured according to ASTM D792, ahardness of about 66 Shore A as measured according to ASTM D2240, a peakmelting temperature of about 59° C. as measured by differential scanningcalorimetry, a flexural modulus of about 10.8 MPa as measured accordingto ASTM D790 (using compression molded samples and tested at 2% secant),a melt flow rate of about 5.0 g/10 min as measured according to ASTMD1238 at 190° C./2.16 kg, a tensile strength at 100% strain of about 2.3MPa as measured according to ASTM D638 at a strain rate of 510 mm/min, atensile strength at break of about 5.7 MPa as measured according to ASTMD638 at a strain rate of 510 mm/min, a tensile elongation at break ofabout 1100% as measured according to ASTM D638 at a strain rate of 510mm/min, and a Vicat softening point of about 37° C. as measuredaccording to ASTM D1525.

S/LEP-C is a copolymer containing about 59 wt. % ethylene monomer unitsand about 41 wt. % octane monomer units. This ethylene elastomer has aspecific gravity of about 0.870 as measured according to ASTM D792, ahardness of about 72 Shore A as measured according to ASTM D2240, a peakmelting temperature of about 60° C. as measured by differential scanningcalorimetry, a flexural modulus of about 12.1 MPa as measured accordingto ASTM D790 (using compression molded samples and tested at 2% secant),a melt flow rate of about 30 g/10 min as measured according to ASTMD1238 at 190° C./2.16 kg, a tensile strength at 100% strain of about 3.3MPa as measured according to ASTM D638 at a strain rate of 510 mm/min, atensile elongation at break of about 1000% as measured according to ASTMD638 at a strain rate of 510 mm/min, and a Vicat softening point ofabout 41° C. as measured according to ASTM D1525.

Elastomer-A is a propylene-ethylene copolymer containing about 15 wt. %ethylene monomer units and about 85 wt. % propylene units. Elastomer-Ahas a specific gravity of about 0.876 as measured according to ASTMD792, a durorneter hardness of about 72 Shore A and about 19 Shore D asmeasured according to ASTM D2240, a peak melting temperature expectedbetween about 30° C. and about 50° C. as measured by differentialscanning caiorirnetry, a crystaliinity of about 14% as measured bydifferential scanning caiorirnetry (@10° C./min), a flexural modulus ofabout 8 MPa as measured according to ISO 178 (using injection moldedsamples and tested at 1% secant), a melt flow rate of about 8 g/10 minas measured according to ASTM D1238 at 230° C./2.16 kg, a tensile stressat yield of about 1.5 MPa as measured according to ISO 527-1,-2, atensile stress at break of about 2.05 MPa as measured according to ISO527-1,-2, end a tensile elongation at break of about 250% as measuredaccording to ISO 527-1,-2.

Elastomer-B is a propylene-ethylene copolymer containing about 9 wt. %ethylene monomer units and about 91 wt. % propylene units. Elastomer-Bhas a specific gravity of about 0.863 as measured according to ASTMD792, a durometer hardness of about 95 Shore A and about 43 Shore D asmeasured according to ASTM D2240, a peak melting temperature expected atabout 85° C. as measured by differential scanning calorimetry, acrystallinity of about 30% as measured by differential scanningcaionmetry (@10° C./min), a flexural modulus of about 105 MPa asmeasured according to ISO 178 (using injection molded samples and testedat 1% secant), a melt flow rate of about 8 g/10 min as measuredaccording to ASTM D1238 at 230° C./2.16 kg, a tensile stress at yield ofabout 7.0 MPa as measured according to ISO 527-1,-2, a tensile stress atbreak of about 15.5 MPa as measured according to ISO 527-1,-2, a tensileelongation at break of greater than about 640% as measured according toISO 527-1,-2, and a Vicat softening point of about 64° C. as measuredaccording to ASTM D1525.

Elastomer-C is a propylene-ethylene copolymer containing about 5 wt. %ethylene monomer units and about 93 wt. % propylene units. Elastomer-Chas a specific gravity of about 0.888 as measured according to ASTMD792, a durometer hardness of about 96 Shore A and about 54 Shore D asmeasured according to ASTM D2240, a peak melting temperature expected atabout 115° C. as measured by differential scanning calorimetry, acrystallinity of about 44% as measured by differential scanningcalorimetry (@10° C./min), a flexural modulus of about 400 MPa asmeasured according to ISO 178 (using injection molded samples and testedat 1% secant), a melt flow rate of about 8 g/10 min as measuredaccording to ASTM D1238 at 230° C./2.16 kg, a tensile stress at yield ofabout 16 MPa as measured according to ISO 527-1,-2, a tensile stress atbreak of about 23 MPa as measured according to ISO 527-1,-2, a tensileelongation at break of greater than about 630% as measured according toISO 527-1,-2, and a Vicat softening point of about 98° C. as measuredaccording to ASTM D1525.

Elastomer-D is a propylene-ethylene copolymer containing about 12 wt. %ethylene monomer units and about 88 wt. % propylene units. Elastomer-Dhas a specific gravity of about 0.864 as measured according to ASTMD792, a durometer hardness of about 70 Shore A as measured according toASTM D2240, a peak melting temperature expected at about 50° C. asmeasured by differential scanning calorlmetry, a crystallinity of about14% as measured by differential scanning calorimetry (@10° C./min), aflexural modulus of about 32 MPa as measured according to ISO 178 (usinginjection molded samples and tested at 1% secant), a melt flow rate ofabout 25 g/10 min as measured according to ASTM D1238 at 230° C./2.16kg, a tensile stress at yield of about 2.8 MPa as measured according toISO 527-1,-2, a tensile elongation at break of greater than about 67% asmeasured according to ISO 527-1,-2, and a Vicat softening point of lessthan bout 30° C. as measured according to ASTM D1525.

Elastomer-E is a propylene-ethylene copolymer containing greater thanabout 9 wt. % ethylene monomer units and about 91 wt. % propylene units.Elastomer-E has a specific gravity of about 0.876 as measured accordingto ASTM D792, a durometer hardness of about 94 Shore A and about 42Shore D as measured according to ASTM D2240, a peak melting temperatureexpected at about 80° C. as measured by differential scanningcalorimetry, a crystallinity of about 29% as measured by differentialscanning calorimetry (@10° C./min), a flexural modulus of about 108 MPaas measured according to ISO 178 (using injection molded samples andtested at 1% secant), a melt flow rate of about 25 g/10 min as measuredaccording to ASTM D1238 at 230° C./2.16 kg, a tensile stress at yield ofabout 7 MPa as measured according to ISO 527-1,-2, a tensile stress atbreak of about 12 MPa as measured according to ISO 527-1,-2, a tensileelongation at break of greater than about 630% as measured according toISO 527-1,-2, and a Vicat softening point of about 60° C. as measuredaccording to ASTM D1525.

PP-A is a polypropylene homopotymar which contains at least 95 wt. %isotaciic polypropylene. PP-A has a density of about 0.900 g/cm³ asmeasured according to ISO 1183, a Charpy notched impact strength at 23°C. of about 2.5 KJ/m² as measured according to ISO 179/eA, a peakmelting temperature greater than about 160° C. as measured bydifferential scanning calorimetry, an expected crystaiiinity of greaterthan about 50% as measured by differential scanning calorimetry, aflexural modulus of about 1650 MPa as measured according to ISO 178, amelt flow rate of about 52 g/10 min as measured according to ISO 1133 at230° C./2.16 kg, a tensile stress at yield of about 37.0 MPa as measuredaccording to ISO 527-1,-2, a tensile elongation at yield of about 9% asmeasured according to ISO 527-1,-2, and a Vicat softening point of about156° C. as measured according to ASTM D1525.

PP-B is a polypropylene homopotymar which contains at least 95 wt. %isotactic polypropylene. PP-B has a density of about 0.90 g/cm³ asmeasured according to ISO 1183, a Charpy notched impact strength at 23°C. of about 2.5 kJ/m² as measured according to ISO 179-1/1 eA, a peakmelting temperature greater than about 156° C. as measured bydifferential scanning calorimetry, an expected crystaiiinity of greaterthan about 50% as measured by differential scanning calorimetry, aflexural modulus of about 1650 MPa as measured according to ISO 178, amelt flow rate of about 52 g/10 min as measured according to ISO 1133 at230° C./2.16 kg, a tensile strength at yield of about 37 MPa as measuredaccording: to ISO 527-2, a tensile elongation at yield of about 9% asmeasured according fo ISO 527-2, and a Vicat softening point of about152° C. as measured according to ASTM D1525.

PP-C is a polypropylene impact copolymer which contains an isotacticpolypropylene phase and an elastomeric copolymer phase. PP-A has adensity of about 0.900 g/cm⁵ as measured according to ISO 1183, a Charpynotched impact strength at 23° C. of about 4 KJ/m³ as measured accordingto ISO 179/eA, a peak malting temperature greater than about 152° C. asmeasured by differential scanning calorlmetry, an expected crystalllnltyof greater than about 45 wt. % as measured fey differential scanningcalorimetry, a flexurel modulus of about 1450 klPa as measured accordingto ISO 178, a melt flow rate of about 44 g/10 min as measured accordingfo ISO 1133 at 230° C./2.16 kg, a tensile stress at yield of about 28.0MPa as measured according to ISO 527-1,-2, a tensile elongation at yieldof about 7% as measured according to ISO 527-1,-2, and a Vical softeningpoint of about 152° C. as measured according to ASTM D1525.

PP-D is an impact polypropylene fsomopolymer which contains at least 80wt. % isotactic polypropylene and an elastomeric copolymer phase. PP-Chas a density of about 0.90 g/cm³ as measured according to ISO 1183, aCharpy notched impact strength at 23° C. of about 10 kJ/m² as measuredaccording to ISO 179-1/1eA, a peak melting temperature greater thanabout 156° C. as measured by differential scanning calorimetry, anexpected crystallinity of greater than about 45 wt. % as measured bydifferential scanning calorimetry, a flexural modulus of about 1450 MPaas measured according to ISO 178, a melt flow rate of about 12 g/10 minas measured according to ISO 1133 at 230° C./2.16 kg, a tensile strengthat yield of about 28 MPa as measured according to ISO 527-2, a tensileelongation at yield of about 8% as measured according to ISO 527-2, anda Vicat softening point of about 152° C. as measured according to ASTMD1525.

CC-A is a color concentrate. CC-B and CC-C are color concentrates whichcontain a colorant, a UV stabilizer and a slip agent in a polypropylenecarrier.

Reinforcement Concentrate-A is a concentrate containing about 60 wt. %long glass fibers and about 40 wt. % PP-B.

Reinforcement Concentrate-B, Reinforcement Coneentrate-C, andReinforcement Concentrate-D each include about 60 wt. % long glassfibers, about 2 wt. % coupling agent, about 36 wt. % polypropylenehaving a melt flow rate greater than about 40 g/10 min (tested accordingto ISO 1133 at 230° C./2.16 kg, such as PP-B), and a heat stabilizers ata concentration of less than about 2 wt. %.

TABLE 3 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. method unit 16 17 18 19 2021 22 23 24 COMPOSITIONS Reinforcement wt % 42 42 42 42 34 42 42Concentrate B Reinforcement wt % 42 Concentrate C Talc wt % 20 S/LEP-Awt % 27 30 S/LEP-B wt % 34 34 35 20 S/LEP-C wt % 27 27 Elastomer-B wt %25 PP-C (copoly) wt % 24 20 27 56 PP-B (homo) wt % 27 20 37 27 33 CC-Bwt % 4 4 4 4 4 4 4 4 4 Total wt % 100 100 100 100 100 100 100 100 100PROPERTIES Ethylene Content wt % 58.7 58.7 58.8 58.8 58.8 58.6 58.6 1558.8 in S/LEP or Elestomer-B Notched Charpy ISO kJ/m² 24 30 23 19 12 8.836 23 35 impact strength 179- at about 23° C. 1eU Average Flexural ISO178 MPa 2128 1929 2185 1569 2132 1995 1739 2252 1500 Modulus HeatDistortion ISO 75 ° C. 112 96 90 81 117 100 80 80 53 Temperature 1.82Vicat Softening ISO ° C. 156 144 146 123 157 147 137 162 115 Point 306AGloss 60° (N111 ASTM GU 1.1 1.1 1.1 1.1 1.2 1.2 1.3 1.1 1.4 texture withD-542 micro matt) gloss 85° (N111 ASTM GU 0.8 0.8 0.7 0.7 0.9 0.9 1 0.81.2 texture with D-542 micro matt) gloss 85° ASTM GU 1.5 1.5 1.5 1.6 1.61.5 1.6 1.5 1.9 (MT10407 Volvo D-542 grain) Mar 6N, 60° GMW dGU 0.3 0.20.3 0.3 0.4 0.3 0.3 0.3 0.8 (N111 texture 14688 with micro matt) Mar 6N,85° GMW dGU 0.9 0.8 0.9 0.8 1.1 0.8 0.7 0.8 1.1 (N111 texture 14688 withmicro matt) scratch - 18 N PV3952 dL −0.1 −0.1 0 0 0 1.9 1.2 0.2 0.3(MT10407

The first polymeric component, the second polymeric component, and thereinforcement concentrate are dry blended and introduced into a Demag100 injection molding machine, in which they are melt-blended prior toinjection into a mold cavity for forming the test samples. The data inTABLE 3 illustrates the expected results. C.E. 24, which does notcontain the long glass fibers has a low heat distortion temperature anda low Vicat softening point, as well as inferior, gloss, scratchresistance, and mar resistance properties.

D9100.05, D8507.15, and D9530.05 are ethylene/α-olefin interpolymerswhich are block having at least one hard block and at least plurality ofsoft block. These block copolymers are available commercially from DowChemical Company under the tradename INFUSE™ and contain ethylene andoctene monomers. The properties of these interpolymers are given inTABLE 4 below.

Examples 25 Through 31

Molded parts are prepared by injection molding the compositions of TABLE5 using the same method as used in EXAMPLES 7 through 15. In EX. 25-31,the second polymeric component is a propylene-ethylene elastomer.

The first polymeric component, the second polymeric component, and thereinforcement concentrate are dry blended and introduced into a Demag100 injection molding machine, in which they are melt-blended prior toinjection into a mold cavity for forming the test samples. The data inTABLE 5 illustrates the expected results.

TABLE 4 Ethylene/α-olefin Interpolymer - Block Copolymer Property, TestMethod (Units) D9100.05 D9507.15 D9530.05 Melt Flow Rate,ASTM 1 5 5D1238 @190° C./ 2.15 kg (g/10 min) Durometer Hardness, ASTM 75 59 86D2240 (Shore A) Concentration of Hard Blocks 27.3 12.4 40.8 (wt. %)Comonomer type octene octene octene Density, ASTM D792 (g/cm³) 0.88 0.870.89 Flexural Modulus 2% secant, ASTM 19 14 56 D790 (MPa) MeltingTemperature, DSC @10° C./ 120 119 119 min (° C.) Ultimate TensileElongation, ASTM 2510 1607 701 D638 (%)

TABLE 5 EX. EX. EX. EX. EX. EX. EX. 25 26 27 28 29 30 31 IngredientReinforcement Concentrate-D 42 42 42 42 42 42 42 D9500.01 30 40 D9507.1530 40 D9530.05 30 30 40 PP-B 24 14 24 14 24 14 PP-C 24 CC-B 4 4 4 4 4 44 Total, wt. % 100 100 100 100 100 100 100 Property, Method (Units)Notched Charpy Impact Strength at 16 25 22 22 20 26 21 about 23° C., ISO179 1eU (kJ/m²) Notched Charpy Impact Strength at 12 19 19 19 9 12 10about −20° C., ISO 179 1eU (kJ/m²) Average Flexural Modulus, ISO 1782017 1254 1947 1196 2078 1644 1483 (MPa) Heat Distortion Temperature@1.8 MPa, 95.2 72.3 99.9 63.5 108 104 93 ISO 75 (° C.) Vicat SofteningPoint, ISO 306A (° C.) 139.1 98.7 144 99 142 129 118 Scratch 18N MT10407, ASTM D-542 0.0 −0.5 0.4 0.1 0 0 −0.4 (dL) Mar 7N N111 @85°, ASTMD-842 (dGU) 0.7 0.5 0.7 0.4 0.4 0.4 0.4 Gloss N111 @85°, ASTM D-542 (GU)0.8 0.8 0.8 0.8 0.9 0.8 0.8

Examples 32 Through 35

Molded parts are prepared by injection molding the compositions of TABLE8 using the same method as used in EXAMPLES 32 includes apropylene-ethylene elastomer, EX. 33 includes an S/LEP, EX. 34 includesa block copolymer, and EX. 35 includes Nordel™ IP4770P elastomer,commercially available from The Dow Chemical Company.

Nordel™ IP4770P is an ethylene propylene diene polymer (EPDM rubber)containing about 70 wt. % ethylene, about 25 wt. % propylene and about 5wt. % of a diene (such as ethylidenenorbornene). Nordel IP4770P is arandom copolymer and has a Mooney Viscosity of about 70 as measuredaccording to ASTM D1646 at ML1_4@125° C. (and an expected melt index asmeasured according to ISO 1133 at 190° C./2.16 kg of less than about 0.2g/10 min).

The first polymeric component, the second polymeric component, and thereinforcement concentrate are dry blended and introduced into a Demag100 injection molding machine, in which they are melt-blended prior toinjection into a mold cavity for forming the test samples. The data inTABLE 6 illustrates the expected results.

TABLE 6 EX. EX. EX. C.E. 32 33 34 35 Ingredient ReinforcementConcentrate-D 42 42 42 42 S/LEP B (ethylene-octene) 34 Elastomer-B(propylene-ethylene) 54 Infuse D9100.05 (ethylene-propylene blockcopolymer) 30 Nordel IP 4770P (EPDM) 40 PP-B (PP homopolymer, 52 MFR) 2024 14 CC-B (color concentrate) 4 4 4 4 Total, wt. % 100 100 100 100Property, Method (Units) Charpy Impact Strength at RT, ISO 179 1eU(kJ/m²) 29 19 16 20 Average Flexural Modulus, ISO 178 (MPa 1559 15692017 1825 Heat Distortion Temperature @1.8 MPa, ISO 75 (° C.) 66 81 9584 Vicat Softening Point, ISO 306A (° C.) 124 123 139 127 Gloss N111@85°, ASTM D-542 (GU) 0.6 0.7 0.8 0.6 Mar 7N N111 @85°, ASTM D-542 (dGU)0.5 0.8 0.7 0.3 Scratch 18N MT, 10407ASTM D-542 (dL) 0.1 0.0 0.1 0.8

Examples 36 Through 39 and Comparative Example 40

Molded parts are prepared by injection molding the compositions of TABLE7 using the same method as used in EXAMPLES 7-15. EXAMPLE 36 includes apropylene-ethylene elastomer, and EXAMPLES. 37-39 includes an S/LEP.C.E, 40 contains SOFTELL CA02A, which is a rubbery C₂-C₃ copolymerhaving a C2 content of about 40 wt. % and a C₃ content of about 60 wt. %and is obtainable from Bassell in Italy. These Examples also include acolor concentrate (CC-C), Orevac CA® 100 which is a maleic anhydridegrafted polypropylene available from Arkema Inc (Philadelphia, Pa.,USA), and CMPP 13.00 is a concentrate of an additives package includinga heat stabilizer in a thermoplastic carrier.

The first polymeric component, the second polymeric component, the glassfibers, the maleic grafted PP, the color concentrate and the additivespackage concentrate are compounded in a twin screw extruder to blendmelt-blend the materials, and then extruded into pellets or granules.The pellets or granules are then introduced into a Demag 100 injectionmolding machine, in which they are melted prior fo injection into a moidcavity for forming the test samples.

TABLE 7 EX. 36 EX. 37 EX. 38 EX. 39 C.E. 40 CS EC 13 636, glass 24.9624.96 24.96 20.16 24.96 fibers Elastomer-A 24.96 S/LEP-C 23.04 S/LEP-B28.80 30.72 SOFTELL CA02A 33.60 PP-B 43.78 PP-D 46.66 40.90 36.10 PP-C43.78 Orevac ® CA100 1.92 0.96 0.96 0.96 0.96 CMPP 13.00 0.38 0.38 0.380.38 0.38 CC-C 4.00 4.00 4.00 4.00 4.00 100.00 100.00 100.00 100.00100.00

TABLE 8 Property, Method (Units) EX. 36 EX. 37 EX. 38 EX. 39 C.E. 40Density, g/cm³ 1.08 Melt Flow Rate, ISO 1133 230° C./2.16 kg 13.9 8.96.1 14 2.3 (g/10 min) n, Charpy Impact @RT, ISO 179 1eU 24 30 37 30 27(kJ/m²) Average Flexural Modulus, ISO 178 (MPa 1630 1630 1301 1124 1455Heat Distortion Temperature @1.8 MPa, 57 53 48 51 52 ISO 75 (° C.) VicatSoftening Temperature, ISO 306A 154 131 126 114 142 (° C.) Gloss beforeMar @85°, ASTM D-542 (GU) 1.0 0.9 0.9 0.9 1.0 Mar 7N N111 @85°, ASTMD-542 (dGU) 0.5 0.3 0.3 0.4 0.6 Gloss N111 MM@85°, ASTM D-542 (GU) 1.21.3 1.3 1.2 1.1 Gloss MT10407 @85°, ASTM D-542 (GU) 1.5 1.5 1.5 1.5 1.3Scratch 18N MT 10407, ASTM D-542 (dL) 0.0 −0.5 −0.7 −0.2 0.2

The data in TABLE 8 illustrates the expected results for EXAMPLES 36-39and COMPARATIVE EXAMPLE 40. Comparative Example 40 requires a highconcentration of the SOFTELL CA02A to achieve a flexural moduluscomparable to the flexural modulus of the samples containing thepropylene elastomer or the S/LEP. Comparative Example 40 also has anundesirably low melt flow rate. The higher melt flow rates of EXAMPLES38-39 are preferred for these polymedo compositions.

It should be understood that various ingredients may be substituted,added, or removed from the above formulations without departing from thescope of the present invention. Moreover, it is contemplated that theweight percentages of the above ingredients and the values of theproperties listed may vary up to or greater than 5%, 10%, 25%, or 50% ofthe values listed. For example, a value of 10 may vary by 10%, which mayresult in a range of about 9 to about 11.

Any numerical values recited herein include all values from the lowervalue to the upper value in increments of one unit provided that thereis a separation of at least 2 units between any lower value and anyhigher value. As an example, if it is stated that the amount of acomponent or a value of a process variable such as, for example,temperature, pressure, time and the like is, for example, from 1 to 90,preferably from 20 to 80, more preferably from 30 to 70, it is intendedthat values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. areexpressly enumerated in this specification. For values which are lessthan one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 asappropriate. These are only examples of what is specifically intendedand all possible combinations of numerical values between the lowestvalue and the highest value enumerated are to be considered to beexpressly stated in this application in a similar manner. As can beseen, the teaching of amounts expressed as “parts by weight” herein alsocontemplates the same ranges expressed in terms of percent by weight.Thus, an expression in the Detailed Description of the invention of arange in terms of at “x′ parts by weight of the resulting polymericblend composition” also contemplates a teaching of ranges of samerecited amount of “x” in percent by weight of the resulting polymericblend composition.”

Unless otherwise stated, all ranges include both endpoints and allnumbers between the endpoints. The use of “about” or “approximately” inconnection with a range applies to both ends of the range. Thus, “about20 to 30” is intended to cover “about 20 to about 30”, inclusive of atleast the specified endpoints.

The disclosures of all articles and references, including patentapplications and publications, are incorporated by reference for allpurposes. The term “consisting essentially of” to describe a combinationshall include the elements, ingredients, components or steps identified,and such other elements ingredients, components or steps that do notmaterially affect the basic and novel characteristics of thecombination. The use of the terms “comprising” or “including” todescribe combinations of elements, ingredients, components or stepsherein also contemplates embodiments that consist essentially of theelements, ingredients, components or steps.

Plural elements, ingredients, components or steps can be provided by asingle integrated element, ingredient, component or step. Alternatively,a single integrated element, ingredient, component or step might bedivided into separate plural elements, ingredients, components or steps.The disclosure of “a” or “one” to describe an element, ingredient,component or step is not intended to foreclose additional elements,ingredients, components or steps. All references herein to elements ormetals belonging to a certain Group refer to the Periodic Table of theElements published and copyrighted by CRC Press, Inc., 1989. Anyreference to the Group or Groups shall be to the Group or Groups asreflected in this Periodic Table of the Elements using the IUPAC systemfor numbering groups.

As used herein the terms “polymer” and “polymerization” are generic, andcan include either or both of the more specific cases of “homo-” andcopolymer” and “homo- and oopolymerization”, respectively.

It is understood that the above description is intended to beillustrative and not restrictive. Many embodiments as well as manyapplications besides the examples provided will be apparent to those ofskill in the art upon reading the above description. The scope of theinvention should, therefore, be determined not with reference fo theabove description, but should instead be determined with reference tothe appended claims, along with the full scope of equivalents to whichsuch claims are entiled. The disclosures of all articles and references,including patent applications and publications, are incorporated byreference for all purposes. The omission in the following claims of anyaspect of subject matter that is disclosed herein is not a disclaimer ofsuch subject matter, nor should it be regarded that the inventors didnot consider such subject matter to be part of the disclosed inventivesubject matter.

What is claimed is:
 1. A soft-touch feel polymeric compositioncomprising a blend of: i. at least about 20 weight percent and less than55 weight percent of a first polymeric component including a relativelyhard thermoplastic, wherein the first polymeric component is anisotactic polypropylene homopolymer, a random polypropylene copolymer,an impact polypropylene, a high density polyethylene, a low densitypolyethylene, a linear low density polyethylene, a medium densitypolyethylene, or any combination thereof, having a crystaiiinity ofgreater than about 31 weight percent as measured according to ASTMD3418.03; ii. greater than 25 weight percent and less than about 60weight percent of a second polymeric component including a relativelysoft thermoplastic as compared with the first polymeric component,wherein the relatively soft thermoplastic is a lower-α-olefin/α-olefininterpolymer (“LAO/α-olefin interpolymer”) which is a multiblockcopolymer having one or more hard blocks and one or more soft blocks,wherein the one or more hard blocks are A Blocks and the one or moresoft blocks are B blocks, the multiblock copolymer having the structureof (AB)_(n), (AB)_(n)A, or B(AB)_(n), where n is greater than 1; theLAO/α-olefin interpolymer has a density of 0.860 to 0.900 g/cm³; theLAO/α-olefin interpolymer includes a first monomer that is ethylene orpropylene, and a second monomer that is butene or octene, wherein theconcentration of the second monomer is greater than 6 mole percent andless than 30 mole percent, based on the total moles of monomer in theLAO/α-olefin interpolymer; the total amount of the first and secondmonomer is greater than about 95 weight percent, based on the totalweight of the LAO/α-olefin interpolymer; the concentration of the Bblocks is about 50 to about 90 weight percent, based on the total weightof the LAO/α-olefin interpolymer; the concentration of the first monomerin the A blocks is greater than about 95 weight percent, and theconcentration of the second monomer in the B blocks is greater thanabout 8 weight percent; iii. 10 to 40 weight percent glass fibers, basedon the total weight of the polymeric composition, wherein the glassfibers have an average length from about 0.5 to about 5 mm in thecomposition, and a diameter from about 3 to about 100 microns; and iv.less than 5 weight percent of a grafted polypropylene; and wherein theLAO/α-olefin interpolymer has a melt index greater than about 0.2 andless than about 20, as measured according to ASTM D1238 Condition 190°C./2.16 kg when the first monomer is ethylene and ASTM D1238 Condition230° C./2.16 kg when the first monomer is propylene; and the polymericcomposition is characterized by a melt flow rate of at least about 5g/10 min as measured according to ASTM D-1238 Condition 230° C./2.16 kg.2. A polymeric composition of claim 1 wherein the LAO/α-olefininterpolymer has at least three of the hard blocks and at least three ofthe soft blocks.
 3. A polymeric composition of claim 2 wherein theLAO/α-olefin interpolymer is an ethylene/α-olefin interpolymer.
 4. Apolymeric composition of claim 1, wherein theLAO/α-olefin interpolymeris an ethylene/α-olefin interpolymer.
 5. A polymeric composition ofclaim 1, wherein the LAO/α-olefin interpolymer is a propylene/α-olefininterpolymer.
 6. A polymeric composition of claims 4 wherein theLAO/α-olefin interpolymer is a copolymer of ethylene and 1-octene,wherein the sum of the concentrations of the ethylene and 1-octenemonomers is greater than 95 wt. % based on the total weight of theLAO/α-olefin interpolymer.
 7. A polymeric composition of claim 6,wherein the LAO/α-olefin interpolymer is characterized by: a densityfrom about 0.850 to about 0.895 g/cm³, a Shore A hardness from about 15to about 95; and a melt index ratio, I₁₀/I₂, from about 5 to about 35;and a melt index, I₂, from about 0.5 to about 20 g/10 min.
 8. Apolymeric composition of claim 7 wherein the LAO/α-olefin interpolymeris characterized by a polydispersity index, Mw/Mn, defined by the ratioof the weight average molecular weight, Mw, and the number averagemolecular weight, Mn, from about 1.9 to about
 7. 9. A polymericcomposition of claim 7 wherein the LAo/α-olefin interpolymer ischaracterized by a concentration of soft block(s) from about 40 to about95 wt. % based on the total weight of the LAO/α-olefin interpolymer andthe LAO/α-olefin interpolymer is characterized by a weight average blockindex, ABI, from about 0.15 to about 0.8.
 10. A polymeric composition ofclaim 9 wherein the glass fiber is present at a concentration from about5 wt. % to about 40 wt. % based on the total weight of the polymericcomposition.
 11. A polymeric composition of claims 10 wherein the firstpolymer component consists essentially of the isotactic polypropylenehomopolymer.
 12. A process for manufacturing a molded article whereinthe molded article contains a portion having a polymeric composition ofclaim 1, and includes a step of removing the article from a mold.
 13. Aprocess for compounding a polymeric composition of claim 1, wherein theprocess comprises the steps of: i) melt-compounding the first polymericcomponent, the second polymeric component, and the glass fibers to forma melt blended polymeric composition; ii) pelletizing the melt blendedpolymeric composition to form pellets or granules capable of feeding ina molding machine; and iii) placing at least 5 kg of the pellets orgranules in a container.
 14. The polymeric composition of claim 1,wherein the first polymeric component is the isotactic polypropylenehomopolymer, the random polypropylene copolymer, the impactpolypropylene, or any combination thereof; the first polymeric componenthas a melt flow rate from 10 to 100 g/10 min as measured according toISO 1133; and the first monomer of the LAO/α-olefin interpolymer isethylene.
 15. The polymeric composition of claim 14, wherein the firstpolymeric component has a melt flow rate from 20 to 100 g/10 min asmeasured according to ISO 1133; and the second polymeric component is anethylene/octene interpolymer.
 16. The polymeric composition of claim 15,wherein the concentration of the glass fibers in the composition is atleast 20 weight percent, the concentration of the propylene couplingagent in the composition is at least 0.1 weight percent, and thepolymeric composition has a melt flow rate of at least about 5 g/10 minas measured according to ASTM D-1238 at 230° C./2.16 kg.
 17. Aninjection molded article comprising: an insert; and an over-moldedlayer; wherein the overmolded layer includes the polymeric compositionof claim 1; wherein the first polymeric component is a polypropyleneselected from the group consisting of a polypropylene homopolymer, animpact polypropylene, a random polypropylene copolymer of ethylene andpropylene having less than about 5 wt. % ethylene, and any combinationthereof, wherein the polypropylene has a melting temperature greaterthan about 125° C. and is characterized by a melt flow rate from 10 to100 g/10 min as measured according to ISO 1133 at 230° C./2.16 kg. 18.The molded article of claim 17, wherein the first polymeric componenthas a melt flow rate from 20 to 100 g/10 min as measured according toISO 1133; and the second polymeric component is an ethylene/octeneinterpolymer.
 19. The molded article of claim 18, wherein theconcentration of the glass fibers in the composition is at least 5weight percent, the concentration of the propylene coupling agent in thecomposition is at least 0.1 weight percent, and the polymericcomposition has a melt flow rate of at least about 5 g/10 min asmeasured according to ASTM D-1238 at 230° C./2.16 kg.